Comparative theoretical study of the structure and bonding of propyne on the Pt(1 1 1) and Pd(1 1 1) surfaces

Abstract The interaction of propyne with the Pt(1 1 1) and Pd(1 1 1) surfaces has been studied by means of the generalised gradient approach of density functional theory using periodic slab models. For both surfaces, the most stable adsorption mode of propyne is di-σ/π mode where the hydrocarbon is σ-bonded to two metal atoms with some additional π bonding to a third adjacent surface atom. The adsorption geometry is a highly distorted propyne with the C 1 and C 2 in a nearly sp 2 hybridisation. Two equivalent surface structures have been found on Pt and Pd. These correspond to the adsorption on the fcc or hcp hollow sites. The adsorption energies on Pt(1 1 1) and Pd(1 1 1) are predicted to be ∼−197 and −161 kJ mol −1 , respectively. The electronic factors that control the chemisorption have been analysed by means of the projected density of states.

[1]  M. Neurock,et al.  Electronic Factors Governing Ethylene Hydrogenation and Dehydrogenation Activity of Pseudomorphic PdML/Re(0001), PdML/Ru(0001), Pd(111), and PdML/Au(111) Surfaces , 2000 .

[2]  M. Hove,et al.  Evidence for the formation of stable alkylidyne structures from C3 and C4 unsaturated hydrocarbons adsorbed on the Pt(111) single crystal surface , 1982 .

[3]  M. J. Weaver,et al.  Periodic Trends in Electrode-Chemisorbate Bonding: Ethylene on Platinum-Group and Gold Electrodes as Probed by Surface-Enhanced Raman Spectroscopy† , 2001 .

[4]  B. Koel,et al.  A temperature programmed desorption study of the reaction of methylacetylene on Pt(111) and Sn/Pt(111) surface alloys , 1998 .

[5]  R. M. Lambert,et al.  Ethyne Cyclization to Benzene over Cu(110) , 1995 .

[6]  D. P. Woodruff,et al.  The local adsorption structure of acetylene on Cu(lll) , 1993 .

[7]  P. Sautet,et al.  Comparative DFT study of the adsorption of 1,3-butadiene, 1-butene and 2-cis/trans-butenes on the Pt(1 1 1) and Pd(1 1 1) surfaces , 2004 .

[8]  Hafner,et al.  Ab initio molecular dynamics for open-shell transition metals. , 1993, Physical review. B, Condensed matter.

[9]  G. Kresse,et al.  Ab initio molecular dynamics for liquid metals. , 1993 .

[10]  D. P. Woodruff,et al.  Structure determination of propyne and 3,3,3-trifluoropropyne on Cu(111) , 2000 .

[11]  R. Hoffmann.  How Chemistry and Physics Meet in the Solid State , 1987 .

[12]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

[13]  Peter Politzer,et al.  Modern density functional theory: a tool for chemistry , 1995 .

[14]  G. Ertl,et al.  Low temperature formation of benzene from acetylene on a Pd(111) surface , 1983 .

[15]  G. Bond.  Relativistic effects in coordination, chemisorption and catalysis , 2000 .

[16]  D. P. Woodruff,et al.  Photoelectron diffraction study of a catalytically active overlayer: C2H2 on Pd{111} , 1998 .

[17]  F. Illas,et al.  Theoretical study of the structure of propene adsorbed on Pt(111) , 2002 .

[18]  J. Ihm,et al.  Catalytic decomposition of acetylene on Fe(001): A first-principles study , 2002 .

[19]  Morikawa,et al.  CO chemisorption at metal surfaces and overlayers. , 1996, Physical review letters.

[20]  R. M. Lambert,et al.  Cyclization of acetylene over Pd(111): a theoretical study of reaction mechanisms and surface intermediates , 1994 .

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

[22]  G. Somorjai,et al.  Hydrogenation of 1,3-butadiene on platinum surfaces of different structures , 1997 .

[23]  R. M. Lambert,et al.  Chemisorption and reactivity on supported clusters and thin films : towards an understanding of microscopic processes in catalysis , 1997 .

[24]  R. M. Lambert,et al.  Low temperature catalytic chemistry of the Pd(111) surface: benzene and ethylene from acetylene , 1983 .

[25]  G. Pacchioni,et al.  Acetylene on Cu and Pd(111) surfaces: a comparative theoretical study of bonding mechanism, adsorption sites, and vibrational spectra , 1996 .

[26]  Manos Mavrikakis,et al.  Electronic structure and catalysis on metal surfaces. , 2002, Annual review of physical chemistry.

[27]  Notker Rösch,et al.  Metal nanoparticles as models of single crystal surfaces and supported catalysts: Density functional study of size effects for CO/Pd(111) , 2002 .

[28]  Herve Toulhoat,et al.  Adsorption of Unsaturated Hydrocarbons on Pd(111) and Pt(111): A DFT Study , 2003 .

[29]  R. Hoffmann,et al.  A Comparative Study of the Chemisorption of Ethylene on Three Metal Surfaces: Ni(111), Pd(111) and Pt(111) , 1990 .

[30]  J. Whitten,et al.  Theory of chemisorption and reactions on metal surfaces , 1996 .

[31]  L. Kesmodel,et al.  Benzene formation from acetylene on Pd(1 1 1): a high-resolution electron energy loss spectroscopy study , 2000 .

[32]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

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

[34]  G. Somorjai,et al.  Conversion of acetylene to benzene over palladium single-crystal surfaces. 1. The low-pressure stoichiometric and the high-pressure catalytic reactions , 1986 .

[35]  Y. Jugnet,et al.  Buta-1,3-diene and but-1-ene chemisorption on Pt(111), Pd(111), Pd(110) and Pd50Cu50(111) as studied by UPS, NEXAFS and HREELS in relation to catalysis , 1996 .

[36]  T. Gentle,et al.  Acetylene, ethylene, and arene chemistry of palladium surfaces , 1983 .

[37]  R. M. Lambert,et al.  Catalytic coupling of propyne on Cu{111} , 1999 .

[38]  Y. Berthier,et al.  Hydrogenation of 1,3-butadiene on Pt(111): comparison with results on Pt(110) and Pt(100) , 1988 .

[39]  R. Parr.  Density-functional theory of atoms and molecules , 1989 .

[40]  Wolfram Koch,et al.  A Chemist's Guide to Density Functional Theory , 2000 .

[41]  N. Rösch,et al.  Size-effects in the acetylene cyclotrimerization on supported size-selected Pdn clusters (1≤n≤30) , 2000 .

[42]  D. Goodman,et al.  PARTICLE SIZE EFFECTS IN THE ACETYLENE CYCLOTRIMERIZATION ON PLANAR MODEL AL2O3 THIN FILM SUPPORTED PD CLUSTERS , 1997 .