First-principles-based kinetic Monte Carlo simulation of the selective hydrogenation of acetylene over Pd(111)

The kinetics for the selective hydrogenation of acetylene over Pd(111) was investigated by using first-principles-based kinetic Monte Carlo simulations. Density functional theory (DFT) calculations were carried out to obtain intrinsic kinetic data for a Horiuti–Polanyi-type reaction mechanism involving the sequential hydrogenation of acetylene. The results were subsequently used to develop a detailed intrinsic kinetics database that includes the adsorption energies of the reactants, intermediates, and products, the reaction energies and activation barriers of the elementary steps in the proposed reaction mechanism. The DFT-calculated energies and activation barriers were initially performed at lower surface coverages, to probe the intrinsic surface chemistry. Subsequent calculations were carried out at higher coverages, to capture the influence of the local environment on the reaction kinetics, and used to parameterize coarse-grained models that describe adsorbate interactions. A van der Waals force field model and a modified bond order conservation model were subsequently used within the simulation to calculate the local through-space interactions and the lateral through-surface interactions occurring between coadsorbates, respectively, and to assess the influence of the local reaction environment. The intrinsic DFT-derived kinetic data and the coarse-grained reaction environment models were used together in a variable time step kinetic Monte Carlo simulation to track the molecular transformations involved in acetylene hydrogenation over the (111) surface of Pd. The kinetic Monte Carlo simulation method [E.W. Hansen, M. Neurock, Chem. Eng. Sci. 54 (1999) 3411; E.W. Hansen, M. Neurock, J. Catal. 196 (2000) 241; E.W. Hansen, M. Neurock, Surf. Sci. 464 (2000) 91; E.W. Hansen, M. Neurock, J. Phys. Chem. B 105 (2001) 9218] used herein explicitly treats the atomic surface structure, the effects of the local reaction environment, and the reaction conditions on the surface kinetics. The simulated apparent activation energy for acetylene hydrogenation was calculated as 8.0±0.6 kcal/mol8.0±0.6 kcal/mol at PH2=100 TorrPH2=100 Torr and PC2H2=100 TorrPC2H2=100 Torr over the temperature range of 300–500 K, in very good agreement with the value of 9.6 kcal/mol reported from experimental studies over well-defined Pd(111) surfaces [H. Molero, B.F. Bartlett, W.T. Tysoe, J. Catal. 181 (1999) 49]. The reaction orders were calculated as −0.52±0.03−0.52±0.03 for acetylene and 1.16±0.031.16±0.03 for hydrogen, which agree very well with the experimental reaction orders by Molero et al. [H. Molero, B.F. Bartlett, W.T. Tysoe, J. Catal. 181 (1999) 49] of −0.66 and 1.04, respectively. A comparison of the simulations carried out assuming non-interacting adsorbates (hard sphere) and those that include lateral interactions between adsorbates showed that although the overall apparent activation energy was weakly sensitive to the presence of lateral interactions, the surface coverages and intrinsic rates changed considerably due to the presence of lateral interactions. The addition of lateral interactions between coadsorbates was found to be essential in simulating the correct overall selectivity behavior and appropriately predicting the apparent reaction orders with respect to hydrogen and acetylene.

[1]  Donghai Mei,et al.  Screening by kinetic Monte Carlo simulation of Pt-Au(100) surfaces for the steady-state decomposition of nitric oxide in excess dioxygen. , 2005, The journal of physical chemistry. B.

[2]  W. Tysoe,et al.  An Investigation of the Reaction Pathway for Ethylene Hydrogenation on Pd(111) , 2001 .

[3]  A. Datye,et al.  The Influence of Catalyst Restructuring on the Selective Hydrogenation of Acetylene to Ethylene , 2001 .

[4]  G. Somorjai,et al.  The first measurement of an absolute surface concentration of reaction intermediates in ethylene hydrogenation , 1996 .

[5]  D. Duca,et al.  Monte Carlo Simulation of Ethylene Hydrogenation on Pt Catalysts , 1996 .

[6]  R. A. Santen,et al.  A First Principles Analysis of C−H Bond Formation in Ethylene Hydrogenation , 2000 .

[7]  G. D. Waddill,et al.  Vibrational spectroscopy of acetylene decomposition on palladium (111) and (100) surfaces , 1984 .

[8]  W. Tysoe,et al.  On the Reaction Pathway for the Hydrogenation of Acetylene and Vinylidene on Pd(111) , 2000 .

[9]  Monte Carlo simulation of kinetic discontinuities in hydrocarbon hydrogenation reactions , 1997 .

[10]  Andrzej Cybulski,et al.  The kinetic model of hydrogenation of acetylene–ethylene mixtures over palladium surface covered by carbonaceous deposits , 2000 .

[11]  Matthew Neurock,et al.  First-principles-based Monte Carlo methodology applied to O/Rh(100) , 2000 .

[12]  Priyam A. Sheth,et al.  A First-Principles Analysis of Acetylene Hydrogenation over Pd(111) , 2003 .

[13]  J. Dumesic,et al.  Microkinetic analysis of diverse experimental data for ethylene hydrogenation on platinum , 1992 .

[14]  J. N. Andersen,et al.  Adsorption of acetylene and hydrogen on Pd(111) : Formation of a well-ordered ethylidyne overlayer , 1998 .

[15]  Donghai Mei,et al.  Ethylene hydrogenation over bimetallic Pd/Au(111) surfaces: Application of quantum chemical results and dynamic Monte Carlo simulation , 2003 .

[16]  G. Bond,et al.  The selective hydrogenation of acetylene , 1958 .

[17]  Staffan Asplund.  Coke formation and its effect on internal mass transfer and selectivity in Pd-catalysed acetylene hydrogenation , 1996 .

[18]  Gilbert F. Froment,et al.  Dynamics of surfaces and reaction kinetics in heterogeneous catalysis : proceedings of the international symposium, Antwerp, Belgium, September 15-17, 1997 , 1997 .

[19]  A. Borodziński,et al.  Surface Heterogeneity of Supported Palladium Catalyst for the Hydrogenation of Acetylene−Ethylene Mixtures† , 1997 .

[20]  L. Guczi,et al.  Reactions of acetylene during hydrogenation on Pd black catalyst , 1981 .

[21]  R. M. Lambert,et al.  Overlayer structure and kinetic behavior of benzene on palladium(111) , 1993 .

[22]  Alexander Penlidis,et al.  Control policies for an industrial acetylene hydrogenation reactor , 1991 .

[23]  A. Borodziński.  Hydrogenation of acetylene–ethylene mixtures on a commercial palladium catalyst , 1999 .

[24]  T. Halgren.  Merck molecular force field. I. Basis, form, scope, parameterization, and performance of MMFF94 , 1996, J. Comput. Chem..

[25]  G. Bond.  Catalysis By Metals , 1962 .

[26]  M. Polanyi,et al.  Exchange reactions of hydrogen on metallic catalysts , 1934 .

[27]  Matthew Neurock,et al.  First-Principles-Based Monte Carlo Simulation of Ethylene Hydrogenation Kinetics on Pd , 2000 .

[28]  Qingfeng Ge,et al.  First-principles-based kinetic Monte Carlo simulation of nitric oxide decomposition over Pt and Rh surfaces under lean-burn conditions , 2004 .

[29]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[30]  Woo-Jae Kim,et al.  Deactivation behavior of a TiO2-added Pd catalyst in acetylene hydrogenation , 2004 .

[31]  J. Dumesic,et al.  Kinetic study of ethylene hydrogenation , 1991 .

[32]  T. Zambelli,et al.  DIRECT OBSERVATION OF SURFACE REACTIONS OF ACETYLENE ON PD(111) WITH SCANNING TUNNELING MICROSCOPY , 1998 .

[33]  Matthew Neurock,et al.  Predicting lateral surface interactions through density functional theory: application to oxygen on Rh(100) , 1999 .

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

[35]  M. Neurock,et al.  Modeling surface kinetics with first-principles-based molecular simulation , 1999 .

[36]  D. Whan,et al.  Hydrogenation of acetylene in excess ethylene on an alumina-supported palladium catalyst at atmospheric pressure in a spinning basket reactor , 1978 .

[37]  N. Schöön,et al.  Competition between ethyne, ethene and carbon monoxide for the active sites during hydrogenation at transient conditions over supported metal catalysts , 1991 .

[38]  Klaas R. Westerterp,et al.  A kinetic study of the hydrogenation of ethyne and ethene on a commercial Pd/Al2O3 catalyst , 1993 .

[39]  D. Land,et al.  Coverage Effects on the Kinetics of Benzene Formation from Acetylene on Pd(111): A Laser-Induced Thermal Desorption/Fourier Transform Mass Spectrometry Investigation , 1996 .

[40]  W. Tysoe,et al.  The Hydrogenation of Acetylene Catalyzed by Palladium: Hydrogen Pressure Dependence , 1999 .

[41]  M. Neurock,et al.  First-principles based kinetic simulations of acetic acid temperature programmed reaction on Pd(111) , 2001 .

[42]  T. Halgren.  Merck molecular force field. II. MMFF94 van der Waals and electrostatic parameters for intermolecular interactions , 1996 .

[43]  R. M. Lambert,et al.  Photoelectron spectroscopy and heterogeneous catalysis: Benzene and ethylene from acetylene on palladium (111) , 1983 .

[44]  Monte‐Carlo model for the hydrogenation of alkenes on metal catalyst , 1998 .

[45]  Hannes Jonsson,et al.  Reversible work transition state theory: application to dissociative adsorption of hydrogen , 1995 .

[46]  A. S. McLeod.  Monte Carlo simulations of heterogeneous catalytic reactions on highly dispersed supported metal catalysts , 1999 .

[47]  G. Barone,et al.  Hydrogenation of acetylene–ethylene mixtures on Pd catalysts: computational study on the surface mechanism and on the influence of the carbonaceous deposits , 2001 .

[48]  R. Madix,et al.  Selective Hydrogenation and H-D Exchange of Unsaturated Hydrocarbons on Pd(100)-P(1×1)-H(D) , 1995 .

[49]  Y. Inoue,et al.  PRESSURE JUMP AND ISOTOPE REPLACEMENT STUDIES OF ACETYLENE HYDROGENATION ON PALLADIUM SURFACE. , 1971 .

[50]  R. A. Santen,et al.  A density functional theory analysis of the reaction pathways and intermediates for ethylene dehydrogenation over Pd(111) , 2002 .

[51]  L. Guczi,et al.  Reaction routes for hydrogenation of acetylene-ethylene mixtures using a double labelling method , 1981 .

[52]  D. F. Ogletree,et al.  Dissociative hydrogen adsorption on palladium requires aggregates of three or more vacancies , 2003, Nature.