Recent Advances in CuI/IIY: Experiments and Modeling

An overview of the CuI/IIY material is performed on the basis of the results obtained during the last 5 years on their structure (nature of the Cu species, siting, coordination …), their use and reactivity, based on TPR, XRD and various ex situ and in situ spectroscopies such as XAS, IR and EPR. A brief summary of previous work is reported to position these recent advances in the context of three decades of studies devoted to the characterization of these materials. Quantum mechanics modeling of both the structure and reactivity of the material is also reported, providing complementary information. Insights related to the properties of the catalysts obtained recently using this molecular approach are presented to demonstrate that this material behaves as a supermolecule. In addition to its adsorption properties, the zeolite Y is one of the most popular zeolite used in catalysis. When it is exchanged with copper, in selective adsorption processes, it has been shown to be a promising adsorbent in the desulfurization of transportation fuels. In the area of environmental applications, a new catalyst based on CuY zeolite is now used for NOx removal from the tail gas of nitric acid plants. Some selected examples are given to illustrate some of the CuY zeolite properties such as adsorption, deNOx elimination and biomimetic behavior.

[1]  M. Keane,et al.  Catalytic oxidative dehydrogenation over Cu2+ exchanged NaY and KY zeolites , 1990 .

[2]  H. Matsumoto,et al.  Active species of CuY zeolite catalyst in CO oxidation at low temperatures. , 1989 .

[3]  Robert F. Martin,et al.  ENCYCLOPEDIA OF MINERAL NAMES: THIRD UPDATE , 2003 .

[4]  R. T. Yang,et al.  New Sorbents for Desulfurization by π-Complexation: Thiophene/Benzene Adsorption , 2002 .

[5]  G. Stucky,et al.  The reactivity of tetracarbonylnickel encapsulated in zeolite X. A case history of intrazeolite coordination chemistry. , 1985 .

[6]  C. Naccache,et al.  Oxidizing and acidic properties of copper-exchange Y zeolite , 1971 .

[7]  T. Heine,et al.  Molecular dynamics simulations of H2O with sites of CuI-FAU and CuII-FAU , 2005 .

[8]  S. Titinchi,et al.  Liquid-Phase Catalytic Hydroxylation of Phenol Using Cu(II), Ni(II) and Zn(II) Complexes of Amidate Ligand Encapsulated in Zeolite-Y as Catalysts , 2003 .

[9]  D. Srinivas,et al.  Biomimetic Oxidations Using Transition Metal Complexes Encapsulated in Zeolites , 2003 .

[10]  P. Ciambelli,et al.  Lean NOx reduction on Cu-NaY and Cu-HZSM5 zeolites at the spark ignition engine exhaust , 1995 .

[11]  E. Kukulska-Zaja̧c,et al.  The activation of acetylene by Cu+ ions in zeolites studied by IR spectroscopy , 2005 .

[12]  B. Coq,et al.  Selective Catalytic Reduction of Nitric Oxide by Ammonia over Cu-FAU Catalysts in Oxygen-Rich Atmosphere , 1999 .

[13]  F. Ribeiro,et al.  Catalytic oxidation of toluene over CuNaHY zeolites , 2001 .

[14]  A. Delabie,et al.  Local Site Deformations in Zeolites by the Coordination of Cu(II) , 2001 .

[15]  I. E. Maxwell,et al.  Crystal structures and dehydrated divalent-copper-exchanged faujasite , 1975 .

[16]  V. Borovkov,et al.  Investigation of Copper Carbonyl Species Formed upon CO Adsorption on Copper-Exchanged Zeolites by Diffuse Reflectance FTIR , 1999 .

[17]  R. T. Yang,et al.  Denitrogenation of transportation fuels by zeolites at ambient temperature and pressure. , 2004, Angewandte Chemie.

[18]  C. Mahr.  L'Analyse Qualitative et les Réactions en Solution, von G. Charlot. Masson & Cie., Paris 1957. 4. Aufl., XI, 368 S., 91 Abb., geb. ffrs. 3.600.- , 1958 .

[19]  M. Che,et al.  ESR and IR studies on the adsorption and disproportionation of nitric oxide on copper exchanged Y zeolites, and of reduction by carbon monoxide , 1972 .

[20]  G. Hutchings,et al.  Catalytic asymmetric heterogeneous aziridination of styrene using CuHY: effect of nitrene donor on enantioselectivity , 2001 .

[21]  P. Ratnasamy,et al.  EPR and Catalytic Investigation of Cu(Salen) Complexes Encapsulated in Zeolites , 1999 .

[22]  F. Quignard,et al.  From supported homogeneous catalysts to heterogeneous molecular catalysts , 1998 .

[23]  G. Rauhut,et al.  FTIR measurements and quantum chemical calculations of ethylene adsorbed on CuNaY , 2002 .

[24]  M. Keane.  Role of the alkali metal co-cation in the ion exchange of Y zeolites III. Equilibrium properties of the Ni/Cu/NaY and Ni/Cu/KY zeolite systems , 1995 .

[25]  D. Vos,et al.  A CRITICAL OVERVIEW OF THE CATALYTIC POTENTIAL OF ZEOLITE-SUPPORTED METAL-COMPLEXES , 1994 .

[26]  H. Sherry.  The Ion-Exchange Properties of Zeolites. I. Univalent Ion Exchange in Synthetic Faujasite , 1966 .

[27]  J. Richardson.  The effect of faujasite cations on acid sites , 1967 .

[28]  A. Maes,et al.  Ion exchange of synthetic zeolite X and Y with Co2+, Ni2+, Cu2+ and Zn2+ ions , 1975 .

[29]  B. Coq,et al.  POLLUTION ABATEMENT USING ZEOLITES: STATE OF THE ART AND FURTHER NEEDS , 2002 .

[30]  G. Rauhut,et al.  Ethyne adsorbed on CuNaY zeolite: FTIR spectra and quantum chemical calculations , 2003 .

[31]  R. Durand,et al.  The Influence of Cocations H, Na, and Ba on the Properties of Cu−Faujasite for the Selective Catalytic Reduction of NO by NH3: An Operando DRIFT Study , 2004 .

[32]  Hiroshi Takahashi,et al.  Cumene cracking activity of zeolite catalysts: III. Effect of copper(II) ion exchange on the faujasite-type synthetic zeolites , 1972 .

[33]  S. Sivasanker,et al.  Immobilization of a Metal Complex in Y-Zeolite Matrix: Synthesis, X-ray Single-Crystal, and Catalytic Activities of a Copper (Schiff-Base)-Y Zeolite Based Hybrid Catalyst , 2004 .

[34]  R. C. Weast.  CRC Handbook of Chemistry and Physics , 1973 .

[35]  G. Hutchings,et al.  An EPR study on the enantioselective aziridination properties of a CuNaY zeolite , 2001 .

[36]  A. Sinha,et al.  Phenol hydroxylation activity of metal phthalocyanine complexes encapsulated in zeolite-Y , 2003 .

[37]  R. T. Yang,et al.  New Sorbents for Desulfurization of Liquid Fuels by π-Complexation , 2001 .

[38]  C. Lamberti,et al.  Polycarbonylic and polynitrosylic species in CuI-exchanged ZSM-5, β, mordenite and Y zeolites: comparison with homogeneous complexes , 2000 .

[39]  J. Weitkamp,et al.  Zeolites and catalysis , 2000 .

[40]  A. Goursot,et al.  Selective catalytic reduction of NO by NH3 on Cu-faujasite catalysts: an experimental and quantum chemical approach. , 2002, Chemphyschem : a European journal of chemical physics and physical chemistry.

[41]  Young Gul Kim,et al.  TPD Study of Mordenite-Type Zeolites for Selective Catalytic Reduction of NO by NH3 , 1996 .

[42]  L. Gang,et al.  NH3 oxidation to nitrogen and water at low temperatures using supported transition metal catalysts , 2000 .

[43]  V. Dondur,et al.  CO interaction with zeolites studied by TPD and FTIR: transition-metal ion-exchanged FAU-type zeolites , 1999 .

[44]  G. Hutchings,et al.  Catalytic Asymmetric Heterogeneous Aziridination of Styrene Using CuHY/bis(oxazoline): Comments on the Factors Controlling Enantioselectivity , 2003 .

[45]  V. A. Babenko,et al.  Compressor-adsorber with a heat pipe , 1996, Journal of Engineering Physics and Thermophysics.

[46]  A. Bell,et al.  Catalysis by Unique Metal Ion Structures in Solid Matrices : From Science to Application , 2001 .

[47]  P. Ratnasamy,et al.  Structure and catalytic properties of dimeric copper(II) acetato complexes encapsulated in zeolite-Y , 2000 .

[48]  B. K. Speronello,et al.  Selective catalytic reduction of NOx using zeolitic catalysts for high temperature applications , 1992 .

[49]  G. Hutchings,et al.  Heterogeneous Enantioselective Synthesis of a Dihydropyran Using Cu-Exchanged Microporous and Mesoporous Materials Modified by Bis(oxazoline) , 2003 .

[50]  P. Gallezot,et al.  X-ray diffraction study of cupric ion migrations in two Y-type zeolites containing adsorbed reagents , 1972 .

[51]  K. Seff,et al.  Partial structures of solid-state copper(II)-exchanged zeolite Y and its D2O sorption complex by pulsed-neutron diffraction , 1998 .

[52]  P. Jacobs,et al.  Redox behavior of transition metal ions in zeolites. I. Reversibility of the hydrogen reduction of copper Y zeolites , 1975 .

[53]  G. Hutchings.  Promotion in Heterogeneous Catalysis: A Topic Requiring a New Approach? , 2001 .

[54]  A. Delabie,et al.  The Coordination of CuII in Zeolites − Structure and Spectroscopic Properties , 2002 .

[55]  R. T. Yang,et al.  Cu(I)−Y-Zeolite as a Superior Adsorbent for Diene/Olefin Separation , 2001 .

[56]  G. Hutchings,et al.  Observation of the enhancement in enantioselectivity with conversion for the aziridination of styrene using copper bis(oxazoline) complexes. , 2003, Chemical communications.

[57]  R. Schoonheydt.  Transition metal ions in zeolites: siting and energetics of Cu2+ , 1993 .

[58]  J. Turkevich,et al.  Paramagnetic Resonance Absorption of Copper Ions in Porous Crystals , 1965 .

[59]  J Baeyens,et al.  Catalytic combustion of volatile organic compounds. , 2004, Journal of hazardous materials.

[60]  D. Goldfarb,et al.  Fourier transform electron spin echo envelope modulation of a S=1/2, I=5/2 spin system: An exact analysis and a second order perturbation approach , 1992 .

[61]  G. Hutchings,et al.  Catalytic asymmetric heterogeneous aziridination of alkenes using zeolite CuHY with [N-(p-tolylsulfonyl)imino]phenyliodinane as nitrene donor , 1999 .

[62]  P. Ratnasamy,et al.  EPR spectroscopy of copper and manganese complexes encapsulated in zeolites , 2001 .

[63]  R. T. Yang,et al.  Desulfurization of Transportation Fuels by Adsorption , 2004 .

[64]  C. Kemball,et al.  Catalysis on faujasitic zeolites , 1977 .

[65]  Shuichi Kagawa,et al.  Catalytic decomposition of nitric oxide over copper(II)-exchanged, Y-type zeolites , 1981 .

[66]  G. Hutchings,et al.  Catalytic heterogeneous aziridination of styrene using CuHY catalyst: an assessment of catalyst stability , 2001 .

[67]  Van Santen,et al.  Selective Low Temperature NH3 Oxidation to N2 on Copper-Based Catalysts , 1999 .

[68]  Nathalie Tanchoux,et al.  Kinetics of the selective catalytic reduction of NO by NH3 on a Cu-faujasite catalyst , 2004 .

[69]  K. P. Jong,et al.  Industrial applications of zeolite catalysis , 1994 .

[70]  P. Gélin,et al.  Infrared study of rhodium clusters entrapped within zeolites , 1979 .

[71]  G. Hutchings,et al.  Aziridination of styrene: comparison of [N-(p-tolylsulfonyl)imino]phenyliodinane and chloramine-T as nitrene donors , 2002 .

[72]  B. Coq,et al.  Influence of co-cations in the selective catalytic reduction of NO by NH3 over copper exchanged faujasite zeolites , 2000 .

[73]  F. d’Acapito,et al.  CuI-Y and CuII-Y zeolites: a XANES, EXAFS and visible-NIR study , 1997 .

[74]  A. Goursot,et al.  A Theoretical Study of Cu(II) Sites in a Faujasite-Type Zeolite: Structures and Electron Paramagnetic Resonance Hyperfine Coupling Constants , 2002 .

[75]  A. Bérces,et al.  Solvation of Cu2+ in Water and Ammonia. Insight from Static and Dynamical Density Functional Theory , 1999 .

[76]  E. F. Souza-Aguiar,et al.  Location of cerium and lanthanum cations in CeNaY and LaNaY after calcination , 1997 .

[77]  I. Mochida,et al.  Catalytic oxidation of propylene over Cu(II)-Y molecular sieve , 1969 .

[78]  N. Walker,et al.  [Cu.(H2O)n]2+ Clusters: The First Evidence of Aqueous Cu(II) in the Gas Phase , 1997 .

[79]  J. Richardson.  Crystal field effects in ion-exchanged faujasites , 1967 .

[80]  J. Baeyens,et al.  Removal of PCDD/F from Incinerator Flue Gases by Entrained-Phase Adsorption , 2002, Journal of the Air & Waste Management Association.

[81]  L. Rees,et al.  Szilard–Chalmers cation recoil studies in zeolites X and Y. Part 1.—Ion exchange in zeolites X and Y , 1976 .

[82]  N. Yamazoe,et al.  Catalytic reduction of NO with ammonia over Cu(II) NaY , 1978 .

[83]  G. Hutchings,et al.  Heterogeneous enantioselective catalyzed carbonyl- and imino-ene reactions using copper bis(oxazoline) zeolite Y. , 2004, Angewandte Chemie.

[84]  S. Titinchi,et al.  Oxidation of phenol with H2O2 catalysed by Cu(II), Ni(II) and Zn(II) complexes of N, N'-bis-(salicylidene)diethylenetriamine (H2saldien) encapsulated in Y-zeolite , 2003 .

[85]  D. Ristoiu,et al.  EPR study of some copper heterocyclic azomethine complexes adsorbed on X and Y zeolites , 1999 .

[86]  S. Koner,et al.  Novel chromotropism and catalytic activities of Cu(Schiff-base) moiety immobilized in Y-zeolite matrix , 2004 .

[87]  Jacob K. Chacko,et al.  Zeolite-encapsulated Co(II), Ni(II) and Cu(II) complexes as catalysts for partial oxidation of benzyl alcohol and ethylbenzene , 2004 .

[88]  M. Keane.  The role of the alkali metal co-cation in the ion exchange of Y zeolites IV. Cerium ion exchange equilibria , 1995 .

[89]  Jerzy Datka,et al.  TPD–IR studies of CO desorption from zeolites CuY and CuX , 2005 .

[90]  M. Che,et al.  EPR as a Tool To Investigate the Transition Metal Chemistry on Oxide Surfaces. , 1997, Chemical reviews.

[91]  J. Uytterhoeven,et al.  Location of cations in synthetic zeolites–X and –Y. Part 5.—The cation distribution in Ca–Y, Ca–X and La–Y in the ultimate stages of dehydration , 1978 .

[92]  B. Weckhuysen,et al.  Study of the coordination of Cu2+ in zeolite Y: Interaction with water and ammonia , 2000 .

[93]  L. Rees,et al.  Calcination of cerium(III) exchanged Y zeolite , 1987 .

[94]  R. T. Yang,et al.  Desulfurization of commercial liquid fuels by selective adsorption via π-complexation with Cu(I)-Y zeolite , 2003 .

[95]  M. Rosseinsky,et al.  Structural Characterization of the Redox Behavior in Copper-Exchanged Sodium Zeolite Y by High-Resolution Powder Neutron Diffraction , 2002 .

[96]  S. T. King,et al.  Reaction Mechanism of Oxidative Carbonylation of Methanol to Dimethyl Carbonate in Cu–Y Zeolite , 1996 .

[97]  R. Car,et al.  First solvation shell of the Cu(II) aqua ion: evidence for fivefold coordination. , 2001, Science.

[98]  G. Charlot.  L'analyse qualitative et les réactions en solution , 1957 .

[99]  R. T. Yang,et al.  Desulfurization of Transportation Fuels with Zeolites Under Ambient Conditions , 2003, Science.

[100]  G. Wulff.  Molecular Imprinting in Cross‐Linked Materials with the Aid of Molecular Templates— A Way towards Artificial Antibodies , 1995 .

[101]  Jacob K. Chacko,et al.  Intrazeolite cobalt(II), nickel(II) and copper(II) complexes of 3-formylsalicylic acid for oxidation reactions , 2002 .

[102]  A. Goursot,et al.  Density functional theory modelling EPR spectra of Cu(II) in Y zeolite , 2002 .

[103]  G. Moretti,et al.  The catalytic activity of Cu-ZSM-5 and Cu-Y zeolites in NO decomposition: dependence on copper concentration , 1994 .

[104]  P. Ratnasamy,et al.  The structural basis for the enhanced oxygenase activity of copper acetate dimers encapsulated in zeolites , 2000 .

[105]  E. Kukulska-Zaja̧c,et al.  IR Studies of the Activation of CC Bond in Alkenes by Cu+ Ions in Zeolites , 2004 .

[106]  C. Moreau,et al.  The Catalysis of the Ruff Oxidative Degradation of Aldonic Acids by Copper(II)-Containing Solids , 2002 .

[107]  J. Lunsford,et al.  Nitric oxide reduction with ammonia over copper(II) Y zeolites , 1976 .

[108]  Catalytic asymmetric heterogeneous ariridination and epoxidation of alkenes using modified microporous and mesoporous materials , 2000 .

[109]  S. Titinchi,et al.  Spectroscopic and catalytic activity study of N, N'-bis(salicylidene)propane-1,3-diamine copper(II) encapsulated in zeolite-Y , 2002 .

[110]  M. Misono,et al.  Comparison of Catalytic Decomposition of Dinitrogen Oxide and Nitrogen Monoxide over Cu/ZSM-5 and Cu/Y Zeolites , 1998 .

[111]  A. Valente,et al.  Oxidation of pinane to 2-pinane hydroperoxide over encaged metal phthalocyanines in Y zeolites. Mechanism and kinetic modelling , 2000 .

[112]  G. Hutchings,et al.  Heterogeneous aziridination of alkenes using Cu2+ exchanged zeolites , 1999 .

[113]  G. Hutchings,et al.  Heterogeneous Catalytic Aziridination of Styrene Using Transition-Metal-Exchanged Zeolite Y , 2001 .

[114]  R. Downing,et al.  Copper-exchanged zeolite catalysts for the cyclodimerization of butadiene: II. Catalyst structure , 1980 .

[115]  J. Richardson.  ESR studies of cationic oxidation sites in faujasite , 1967 .

[116]  W. Sachtler,et al.  Zeolite-Supported Transition Metal Catalysts , 1993 .

[117]  M. Keane,et al.  A catalytic and characterization study of the surface acidity generated on the reduction of copper exchanged Y zeolites , 1990 .

[118]  Xianyong Wei,et al.  Cu2+-Exchanged Zeolites as Catalysts for Phenol Hydroxylation with Hydrogen Peroxide , 2004 .

[119]  I. Halász,et al.  Active sites of H-ZSM5 catalysts for the oxidation of nitric oxide by oxygen , 1995 .

[120]  R. Sheldon,et al.  Liquid phase oxidation at metal ions and complexes in constrained environments , 1998 .

[121]  A. Goursot,et al.  Experimental and theoretical approaches to the study of TMI-zeolite (TM = Fe, Co, Cu) , 2005 .

[122]  G. Hutchings.  Enantioselective Reactions Using Modified Microporous and Mesoporous Materials , 2002 .

[123]  Achim Müller,et al.  SUPRAMOLECULAR INORGANIC CHEMISTRY : SMALL GUESTS IN SMALL AND LARGE HOSTS , 1995 .

[124]  W. Trogler.  Physical properties and mechanisms of formation of nitrous oxide , 1999 .

[125]  G. Hutchings,et al.  Heterogeneous aziridination of styrene using [N-(p-nitrophenylsulfonyl)imino]phenyliodinane as nitrene donor: influence of the reaction parameters on yield and enantioselectivity , 2002 .

[126]  Anil K. Sinha,et al.  Spectroscopic investigation and catalytic activity of copper(II) phthalocyanine encapsulated in zeolite Y , 2000 .

[127]  H. Yahiro,et al.  Magnetic interaction between copper (II) ion and paramagnetic NO and O2 molecules in Y-type zeolite at low temperature: An EPR study , 2005 .

[128]  J. Fraissard,et al.  129Xe NMR overview of xenon physisorbed in porous solids , 1999 .

[129]  E. Kukulska-Zaja̧c,et al.  The activation of CO bond in acetone by Cu+ cations in zeolites: IR studies and quantum chemical DFT calculations , 2005 .

[130]  P. Cox,et al.  The hydrothermal synthesis of zeolites: history and development from the earliest days to the present time. , 2003, Chemical reviews.

[131]  A. Goursot,et al.  Theoretical Modeling of a Copper Site in a Cu(II)−Y Zeolite , 2001 .

[132]  J. S. Lee,et al.  Easily separable molecular catalysis , 2000 .

[133]  H. Matsumoto,et al.  Catalytic behavior and structure of active species on Cu-Y zeolite in oxidation of carbon monoxide , 1990 .

[134]  R. Downing,et al.  Copper-exchanged zeolite catalysts for the cyclodimerization of butadiene: I. Catalyst stability and regenerability , 1980 .

[135]  A. Delabie,et al.  A reinterpretation of the EPR spectra of Cu(II) in zeolites A, Y and ZK4, based on ab initio cluster model calculations , 2001 .

[136]  F. Bedioui.  Zeolite-encapsulated and clay-intercalated metal porphyrin, phthalocyanine and Schiff-base complexes as models for biomimetic oxidation catalysts: an overview , 1995 .

[137]  S. Larsen,et al.  EPR Study of Copper-Exchanged Zeolites: Effects of Correlated g- and A-Strain, Si/Al Ratio, and Parent Zeolite , 2000 .

[138]  B. Imelik,et al.  Structures cristallines de deux zéolithes de type y cériée et protonée, CeHY , 1971 .

[139]  C. Lamberti,et al.  XRD, XAS, and IR Characterization of Copper-Exchanged Y Zeolite , 2000 .

[140]  N. Takezawa,et al.  The reactivity of NO3-type adsorbed species on the decomposition of nitrogen monoxide over copper/Y-zeolites , 1998 .

[141]  J. Smith.  Faujasite-Type Structures: Aluminosilicate Framework: Positions of Cations and Molecules: Nomenclature , 1974 .

[142]  D. Goldfarb,et al.  Interactions of Cu(II) ions with framework Al in high Si:Al zeolite Y as determined from X- and W-band pulsed EPR/ENDOR spectroscopies , 2002 .

[143]  D. Srinivas,et al.  Oxidation of ethylbenzene over “neat” and zeolite-Y-encapsulated copper tri- and tetraaza macrocyclic complexes , 2004 .

[144]  G. Hutchings,et al.  Catalytic Asymmetric Heterogeneous Aziridination Using CuHY/bis(oxazoline): Effect of Reaction Conditions on Enantioselectivity , 2003 .

[145]  Nicholas W. Hurst,et al.  Temperature programmed reduction of copper ions in zeolites , 1979 .

[146]  Martin Kaupp,et al.  A Critical Validation of Density Functional and Coupled-Cluster Approaches for the Calculation of EPR Hyperfine Coupling Constants in Transition Metal Complexes , 1999 .

[147]  R. Eldridge,et al.  Olefin/Paraffin Separations by Reactive Absorption: A Review , 1998 .

[148]  F. Larachi,et al.  Catalytic wet oxidation of high-strength alcohol-distillery liquors , 2000 .