Theoretical studies of stability and reactivity of CHx species on Ni(111)

被引:179
作者
Watwe, RM
Bengaard, HS
Rostrup-Nielsen, JR
Dumesic, JA
Norskov, JK
机构
[1] Univ Wisconsin, Dept Chem Engn, Madison, WI 53706 USA
[2] Tech Univ Denmark, Ctr Atom Scale Mat Phys, DK-2800 Lyngby, Denmark
[3] Haldor Topsoe Res Labs, DK-2800 Lyngby, Denmark
关键词
D O I
10.1006/jcat.1999.2699
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Periodic infinite plane wave slab calculations were performed, in conjunction with density functional theory and ultrasoft pseudopotentials to study the adsorption of CHx (x = 1, 2, 3) species on the Ni(lll) surface. The potential energy diagram is presented for the overall reaction of surface carbon with dihydrogen to methane or, equivalently, the conversion of methane to surface carbon, including all adsorbed intermediates and transition states. All CH, intermediates prefer threefold sites. The transition states involve the formation of C-H bonds on top of a Ni atom, with the reaction coordinate being primarily a C-H stretch. The calculated activation energies to form the C-H bond are near 70-85 kJ/mol for different CH, species. To illustrate the new possibilities offered by detailed potential energy diagrams, the results from the quantum chemical calculations are combined with experimental results in the literature to make initial estimates of kinetic parameters involved in the methanation of CO over nickel. Sensitivity analyses in this region of parameter space are used to assess the effects of these kinetic parameters on the overall rate of methanation. A good description of the experimental methanation reaction kinetics (D. W. Goodman et al., J. Catal. 63, 226 (1980)) is achieved by adjusting the sensitive kinetic parameters within reasonable ranges. The kinetic analyses shows that adsorbed CO and CH are the most abundant species on the surface, and the energies of the transition states to form methyl species from methylene species and to form methane from methyl species appear to control the rate of the overall reaction. (C) 2000 Academic Press.
引用
收藏
页码:16 / 30
页数:15
相关论文
共 44 条
[1]   CO hydrogenation on a nickel catalyst - II. A mechanistic study by transient kinetics and infrared spectroscopy [J].
Agnelli, M ;
Swaan, HM ;
Marquez-Alvarez, C ;
Martin, GA ;
Mirodatos, C .
JOURNAL OF CATALYSIS, 1998, 175 (01) :117-128
[2]   ADSORPTION MICROCALORIMETRY AND STICKING PROBABILITIES ON METAL SINGLE-CRYSTAL SURFACES [J].
ALSARRAF, N ;
STUCKLESS, JT ;
WARTNABY, CE ;
KING, DA .
SURFACE SCIENCE, 1993, 283 (1-3) :427-437
[3]   ON THE KINETICS OF CO METHANATION ON NICKEL SURFACES [J].
ALSTRUP, I .
JOURNAL OF CATALYSIS, 1995, 151 (01) :216-225
[4]  
[Anonymous], AFFINITE
[5]   A detailed theoretical treatment of the partial oxidation of methane to syngas on transition and coinage metal (M) catalysts (M = Ni, Pd, Pt, Cu) [J].
Au, CT ;
Liao, MS ;
Ng, CF .
JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (22) :3959-3969
[6]   A THEORETICAL-MODEL OF HYDROCARBON FORMATION FROM CO AND H-2 [J].
BAETZOLD, RC .
JOURNAL OF PHYSICAL CHEMISTRY, 1984, 88 (23) :5583-5589
[7]   KINETICS OF THE ACTIVATED DISSOCIATIVE ADSORPTION OF METHANE ON THE LOW INDEX PLANES OF NICKEL SINGLE-CRYSTAL SURFACES [J].
BEEBE, TP ;
GOODMAN, DW ;
KAY, BD ;
YATES, JT .
JOURNAL OF CHEMICAL PHYSICS, 1987, 87 (04) :2305-2315
[8]   THERMODYNAMIC AND KINETIC COUPLING OF CHAIN AND CATALYTIC REACTIONS [J].
BOUDART, M .
JOURNAL OF PHYSICAL CHEMISTRY, 1983, 87 (15) :2786-2789
[9]  
BOUDART M, UNPUB CATAL LETT
[10]   METHANE ACTIVATION AND DEHYDROGENATION ON NICKEL AND COBALT - A COMPUTATIONAL STUDY [J].
BURGHGRAEF, H ;
JANSEN, APJ ;
VANSANTEN, RA .
SURFACE SCIENCE, 1995, 324 (2-3) :345-356