Surface science and the silver-catalyzed epoxidation of ethylene: an industrial perspective

Abstract Key surface science studies relating to the silver-catalyzed epoxidation of ethylene are reviewed from the perspective of industrial catalyst development. Fundamental studies using primarily Ag(111) and Ag(110) single crystals have provided evidence for the key role of atomic rather than molecular oxygen in both the epoxidation and combustion reactions. Model studies employing higher alkenes are also discussed as they reveal the importance of C–H bond reactivity in the combustion pathways. The influence of alkali and halide promoter species via electronic and geometric effects is discussed. Recent STM and in situ Raman studies of oxygen, chlorine and CO 2 adsorption on Ag surfaces showing dynamic silver restructuring and the identification of reactive surface species are highlighted as an area that will further the understanding of the epoxidation reaction by providing key structural information. Such information would not only benefit computational modelling efforts, but could also lead to more rational catalyst development processes.

[1]  R. M. Lambert,et al.  ALKALI-METAL PROMOTERS AND CATALYSIS - A SINGLE-CRYSTAL INVESTIGATION OF ETHYLENE EPOXIDATION ON CS-DOPED AG(111) , 1985 .

[2]  M. Paffett,et al.  The role of chlorine promoters in catalytic ethylene epoxidation over the Ag(110) surface , 1984 .

[3]  I. Stensgaard,et al.  THE REACTION OF CARBON DIOXIDE WITH AN OXYGEN PRECOVERED AG(110) SURFACE , 1995 .

[4]  R. M. Lambert,et al.  Molecular mechanism of alkene epoxidation: A model study with 3,3-dimethyl-1-butene on Ag(111) , 1990 .

[5]  R. Schlögl,et al.  In‐situ Raman Studies of Ethylene Oxidation at Ag(111) and Ag(110) under Catalytic Reaction Conditions , 1993 .

[6]  R. M. Lambert,et al.  Alkali metal, chlorine and other promoters in the silver-catalysed selective oxidation of ethylene , 1987 .

[7]  R. Hamers,et al.  Chlorine-Induced Restructuring of Ag(111) Films Observed by Scanning Tunneling Microscopy , 1997 .

[8]  R. M. Lambert,et al.  Electron spectroscopic investigation of ultra-selective ethylene epoxidation: studies with Ag(111) and (110) model systems and with Ag/Al2O3 catalysts , 1992 .

[9]  A. Bradshaw,et al.  Surface Carbonate on Ag{110}: an X-Ray Absorption Fine-Structure Study , 1988 .

[10]  N. Bartelt,et al.  Scanning tunneling microscopy study of the faceting dynamics of stepped Ag(110) upon oxygen exposure , 1994 .

[11]  Jeffrey T. Roberts,et al.  Epoxidation of olefins on silver: conversion of norbornene to norbornene oxide by atomic oxygen on silver(110) , 1988 .

[12]  G. Hoflund,et al.  Study of Cs-promoted, α-alumina-supported silver ethylene-epoxidation catalysts. I: Characterization of the support and As-prepared catalyst , 1996 .

[13]  T. Hashizume,et al.  Scanning tunneling microscopy of oxygen adsorption on the Ag(110) surface , 1992 .

[14]  R. M. Lambert,et al.  Molecular mechanism of heterogeneous alkene epoxidation: A model study with styrene on Ag(111) , 1989 .

[15]  T. Hashizume,et al.  Vibrational and structural studies of oxygen adsorption on the Ag(110) surface , 1994 .

[16]  Robert B. Grant,et al.  A single crystal study of the silver-catalysed selective oxidation and total oxidation of ethylene , 1985 .

[17]  Pai Ww,et al.  Formation of (n x 1)-O/Ag(110) overlayers and the role of step-edge atoms. , 1996 .

[18]  J. Stöhr,et al.  The orientation of the carbonate anion on Ag(110) , 1988 .

[19]  E. Kennedy,et al.  The partial oxidation of norbornene over a silver catalyst under steady state conditions , 1991 .

[20]  Yang Jun,et al.  Promoting effects of Re and Cs on silver catalyst in ethylene epoxidation , 1992 .

[21]  M. Kuhn,et al.  Interaction of Silver, Cesium, and Zinc with Alumina Surfaces: Thermal Desorption and Photoemission Studies , 1996 .

[22]  G. Hoflund,et al.  Study of Cs-promoted, α-alumina-supported silver, ethylene-epoxidation catalysts. II. Effects of aging , 1996 .

[23]  J. Nørskov,et al.  Oxygen chemisorption on metal surfaces: General trends for Cu, Ni and Ag , 1993 .

[24]  C. Campbell Cs-promoted Ag(111): model studies of selective ethylene oxidation catalysts , 1985 .

[25]  Charles T. Campbell,et al.  Chlorine promotion of selective ethylene oxidation over Ag(110): Kinetics and mechanism , 1985 .

[26]  M. Barteau,et al.  Cyclization and related reactions of iodoethanol on Ag(110) , 1997 .

[27]  S. Bebelis,et al.  In SituControlled Promotion of Catalyst Surfaces via NEMCA: The Effect of Na on the Ag-Catalyzed Ethylene Epoxidation in the Presence of Chlorine Moderators , 1996 .

[28]  D. King,et al.  The surface geometry of a caesium induced (1 × 2) multilayer reconstruction of Ag(110) , 1989 .

[29]  N. W. Cant,et al.  The partial oxidation of some cyclohexenes and branched chain olefins over a silver catalyst , 1992 .

[30]  R. M. Lambert,et al.  Secondary chemistry in the selective oxidation of ethylene: Effect of Cl and Cs promoters on the adsorption, isomerisation, and combustion of ethylene oxide on Ag(111) , 1987 .

[31]  R. M. Lambert,et al.  The silver-catalysed decomposition of N2O and the catalytic oxidation of ethylene by N2O over Ag(111) and Agα-Al2O3 , 1987 .

[32]  C. Campbell Chlorine promoters in selective ethylene epoxidation over Ag(111): A comparison with Ag(110) , 1986 .

[33]  R. Schlögl,et al.  Oxygen-induced restructuring of Ag(111) , 1993 .

[34]  D. Sajkowski,et al.  Structure Sensitivity of the Catalytic Oxidation of Ethene by Silver , 1987 .

[35]  Kazue Yamada,et al.  Partial Purification and Product Specificity of Adzukibean Lipoxygenase , 1991 .

[36]  G. H. Twigg The catalytic oxidation of ethylene , 1946 .