Ethylene epoxidation catalyzed by chlorine-promoted silver oxide

It is demonstrated that, on a silver oxide surface, direct formation of ethylene oxide (EO) through the reaction between gas phase ethylene and surface oxygen is possible. The direct reaction channel produces EO selectively without competing with acetaldehyde (AA) formation. The oxometallacycle (OMC) forms on an oxygen vacant surface and reduces EO selectivity. Cl adsorption removes these surface vacant sites and hence prevents the formation of the OMC intermediate.

[1]  Subsurface oxygen and surface oxide formation at Ag(111): A density-functional theory investigation , 2003, cond-mat/0302122.

[2]  Hafner,et al.  Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. , 1994, Physical review. B, Condensed matter.

[3]  G. Henkelman,et al.  Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points , 2000 .

[4]  M. Barteau,et al.  Investigation of Ethylene Oxide on Clean and Oxygen-Covered Ag(110) Surfaces , 2009 .

[5]  A. Alavi,et al.  New insights into ethene epoxidation on two oxidized Ag[111] surfaces. , 2003, Journal of the American Chemical Society.

[6]  W. Sachtler,et al.  The Mechanism of the Selective Oxidation of Ethylene to Ethylene Oxide , 1974 .

[7]  R. Vansanten.  The mechanism of ethylene epoxidation , 1986 .

[8]  Van Santen,et al.  Ethylene epoxidation on silver(110): the role of subsurface oxygen , 2001 .

[9]  M. Scheffler,et al.  Oxide formation at the surface of late 4d transition metals: insights from first-principles atomistic thermodynamics , 2003, cond-mat/0304184.

[10]  D. King,et al.  Specific ethene surface activation on silver oxide covered Ag[111] from the interplay of STM experiment and theory. , 2003, Journal of the American Chemical Society.

[11]  Rutger A. van Santen,et al.  Ethylene Epoxidation Catalyzed by Silver Oxide , 2011 .

[12]  Van Santen,et al.  Reactivity of oxygen adsorbed on silver powder in the epoxidation of ethylene , 1981 .

[13]  S. Linic,et al.  Heterogeneous Catalysis of Alkene Epoxidation , 2008 .

[14]  R. L. Kuczkowski,et al.  The oxidation of ethylene-1,2-d2 over a silver catalyst studied by microwave spectroscopy , 1978 .

[15]  F. Illas,et al.  A theoretical study of coverage effects for ethylene epoxidation on Cu(111) under low oxygen pressure , 2006 .

[16]  K. Honkala,et al.  Formation of gold(I) edge oxide at flat gold nanoclusters on an ultrathin MgO film under ambient conditions. , 2010, Angewandte Chemie.

[17]  B. Bal'zhinimaev,et al.  Size effects in ethylene oxidation on silver catalysts. Influence of support and Cs promoter , 1995 .

[18]  Akimi Ayame,et al.  Supported silver catalysts for the oxidation of ethylene the effects of thermal treatment of alumina as catalyst support , 1979 .

[19]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[20]  G. Deo,et al.  Interaction of Polycrystalline Silver with Oxygen, Water, Carbon Dioxide, Ethylene, and Methanol: In Situ Raman and Catalytic Studies , 1999 .

[21]  R. M. Lambert,et al.  Why copper is intrinsically more selective than silver in alkene epoxidation: ethylene oxidation on Cu(111) versus Ag(111). , 2005, Journal of the American Chemical Society.

[22]  William A. Goddard,et al.  Chemisorption of oxygen, chlorine, hydrogen, hydroxide, and ethylene on silver clusters: A model for the olefin epoxidation reaction , 1989 .

[23]  M. W. Roberts,et al.  XPS study of oxygen adsorption on supported silver : effect of particle size , 1997 .

[24]  W. Goddard,et al.  The surface atomic oxyradical mechanism for Ag-catalyzed olefin epoxidation☆ , 1988 .

[25]  R. M. Lambert,et al.  Mechanism of the silver-catalysed heterogeneous epoxidation of ethylene , 1983 .

[26]  N. W. Cant,et al.  Catalytic oxidation: VI. Oxidation of labeled olefins over silver , 1978 .

[27]  Yang,et al.  Missing-row reconstruction of Ag(110) induced by a 2 x 1) oxygen overlayer. , 1989, Physical review. B, Condensed matter.

[28]  S. Linic,et al.  Shape‐ and Size‐Specific Chemistry of Ag Nanostructures in Catalytic Ethylene Epoxidation , 2010 .

[29]  Ab initio density functional study of O on the Ag(001) surface , 2003, cond-mat/0303351.

[30]  M. Barteau,et al.  The Formation of Epoxides from Reactions of Oxametallacycles on Ag(110): A Density Functional Theory Study , 2001 .

[31]  S. Linic,et al.  Synthesis of Oxametallacycles from 2-Iodoethanol on Ag(111) and the Structure Dependence of Their Reactivity , 2002 .

[32]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[33]  A. Bell,et al.  The relationship of adsorbed species observed by infrared spectroscopy to the mechanism of ethylene oxidation over silver , 1975 .

[34]  S. Linic,et al.  Control of ethylene epoxidation selectivity by surface oxametallacycles. , 2003, Journal of the American Chemical Society.

[35]  P. Mars,et al.  Oxidations carried out by means of vanadium oxide catalysts , 1954 .

[36]  F. Mongeot,et al.  Sub-surface incorporation of oxygen on Ag(001) during molecular dissociation , 1999 .

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

[38]  V. Zaikovskii,et al.  Catalytic and structural properties of ultradispersed silver powder, prepared by a wire explosion technique , 1998 .

[39]  Suljo Linic,et al.  Construction of a reaction coordinate and a microkinetic model for ethylene epoxidation on silver from DFT calculations and surface science experiments , 2003 .

[40]  Wolfgang Ehrfeld,et al.  Silver-catalyzed oxidation of ethylene to ethylene oxide in a microreaction system , 2002 .

[41]  G. Gau,et al.  A cyclic reactor study of ethylene epoxidation , 1983 .

[42]  A. Bell,et al.  Infrared spectra of adsorbed species present during the oxidation of ethylene over silver , 1975 .

[43]  Wenning Wang,et al.  O/Ag(100) surface: A density functional study with slab model , 2002 .

[44]  Singh,et al.  Erratum: Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation , 1993, Physical review. B, Condensed matter.

[45]  Francesc Illas,et al.  Towards an understanding of promoter action in heterogeneously catalyzed ethene epoxidation: Why chlorine is the best halogen , 2008 .

[46]  F. Illas,et al.  The chemistry of chlorine on Ag(111) over the sub-monolayer range: A density functional theory investigation , 2008 .

[47]  Ali Alavi,et al.  Structures and thermodynamic phase transitions for oxygen and silver oxide phases on Ag{1 1 1} , 2003 .

[48]  D. A. Bulushev,et al.  Transient response and infrared studies of ethylene oxide reactions on silver catalysts and supports , 1995 .

[49]  S. Linic,et al.  On the mechanism of Cs promotion in ethylene epoxidation on Ag. , 2004, Journal of the American Chemical Society.

[50]  Tadasu Suzuki.  X-Ray Study on the Binding Properties of Cu 2 O and Ag 2 O Crystals , 1960 .

[51]  G. Henkelman,et al.  A grid-based Bader analysis algorithm without lattice bias , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[52]  Q. Jiang,et al.  A DFT study on electronic structures and catalysis of Ag12O6/Ag(111) for ethylene epoxidation , 2007 .

[53]  A. Bell,et al.  The effect of dichloroethane moderation on the adsorbed species present during the oxidation of ethylene over silver , 1976 .

[54]  Matthias Scheffler,et al.  Experimental and theoretical study of oxygen adsorption structures on Ag(111) , 2009, 0904.3734.

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

[56]  S. Linic,et al.  Engineering selectivity in heterogeneous catalysis: Ag nanowires as selective ethylene epoxidation catalysts. , 2008, Journal of the American Chemical Society.