Consequences of adsorbate-adsorbate interactions for apparent kinetics of surface catalytic reactions

Goswami, Anshuman; Ma, Hanyu; Schneider, William F.

doi:10.1016/j.jcat.2021.12.005

Title: Consequences of adsorbate-adsorbate interactions for apparent kinetics of surface catalytic reactions

Journal Article · 15 December 2021 · Journal of Catalysis

DOI: https://doi.org/10.1016/j.jcat.2021.12.005 · OSTI ID:1835672

Goswami, Anshuman ^[1]; Ma, Hanyu ^[2]; Schneider, William F. ^[2]

Univ. of Notre Dame, IN (United States); University of Notre Dame
Univ. of Notre Dame, IN (United States)

Lateral adsorbate interactions at catalyst surfaces are known to influence adsorption energies and reaction rates. Lattice-based kinetic Monte Carlo (kMC) simulations are able to capture these influences, but such models are typically parameterized for a specific reaction network and catalyst surface. Here we report kMC simulations to probe the influence of lateral interactions on simulated rates, rate orders, apparent activation energies, and Sabatier plots. We construct a simple, two-step reaction network involving a single adsorbate and rate- limiting diatomic dissociation, employ a generic repulsive lateral interaction model consistent with known adsorbate-adsorbate interactions on metal surfaces, and a rate model consistent with known Brønsted-Evans-Polyani relationships for diatomic dissocations. Furthermore, we juxtapose reaction kinetics over a wide range of reaction conditions and catalyst binding energies, as a function of interaction strength. We find that at a given zero-coverage binding energy and external conditions, adsorbate coverage decreases monotonically with increasing interaction strength, but absolute rates can vary linearly or nonlinearly. Interactions flatten the Sabatier volcano and shift the maximum towards stronger binding. Influences on apparent rate orders and activation energies are modest and are sensitive to interaction-induced adsorbate ordering. Model predictions are sensitive to lattice size effects at high coverages. The results, modelled for a simple reaction system, highlight the generic consequences of lateral interactions and guidance for identifying their signatures in observed kinetics.

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Research Organization:: Univ. of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; SC0021107

OSTI ID:: 1835672

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 405; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (66)

Kinetics on ideal and real surfaces Boudart, Michel AIChE Journal, Vol. 2, Issue 1 https://doi.org/10.1002/aic.690020113	journal	March 1956
A Simple Rule of Thumb for Diffusion on Transition-Metal Surfaces Nilekar, Anand Udaykumar; Greeley, Jeff; Mavrikakis, Manos Angewandte Chemie, Vol. 118, Issue 42 https://doi.org/10.1002/ange.200602223	journal	October 2006
DFT-Based Coverage-Dependent Model of Pt-Catalyzed NO Oxidation Getman, Rachel B.; Schneider, William F. ChemCatChem, Vol. 2, Issue 11 https://doi.org/10.1002/cctc.201000146	journal	August 2010
Efficient Implementation of Cluster Expansion Models in Surface Kinetic Monte Carlo Simulations with Lateral Interactions: Subtraction Schemes, Supersites, and the Supercluster Contraction Hess, Franziska Journal of Computational Chemistry, Vol. 40, Issue 30 https://doi.org/10.1002/jcc.26041	journal	August 2019
The Brønsted–Evans–Polanyi Relation and the Volcano Plot for Ammonia Synthesis over Transition Metal Catalysts Logadottir, A.; Rod, T. H.; Nørskov, J. K. Journal of Catalysis, Vol. 197, Issue 2 https://doi.org/10.1006/jcat.2000.3087	journal	January 2001
Universality in Heterogeneous Catalysis Nørskov, J. K.; Bligaard, T.; Logadottir, A. Journal of Catalysis, Vol. 209, Issue 2 https://doi.org/10.1006/jcat.2002.3615	journal	July 2002
NO2 inhibits the catalytic reaction of NO and O2 over Pt Mulla, S. S.; Chen, N.; Delgass, W. N. Catalysis Letters, Vol. 100, Issue 3-4 https://doi.org/10.1007/s10562-004-3466-1	journal	April 2005
Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals Grabow, Lars C.; Hvolbæk, Britt; Nørskov, Jens K. Topics in Catalysis, Vol. 53, Issue 5-6 https://doi.org/10.1007/s11244-010-9455-2	journal	February 2010
Lattice-gas model for description of the adsorbed molecules of two kinds Zhdanov, V. P. Surface Science, Vol. 111, Issue 1 https://doi.org/10.1016/0039-6028(81)90475-1	journal	October 1981
Study of high coverages of atomic oxygen on the Pt(111) surface Parker, Deborah Holmes; Bartram, Michael E.; Koel, Bruce E. Surface Science, Vol. 217, Issue 3 https://doi.org/10.1016/0039-6028(89)90443-3	journal	July 1989
Modeling surface kinetics with first-principles-based molecular simulation Hansen, Eric W.; Neurock, Matthew Chemical Engineering Science, Vol. 54, Issue 15-16 https://doi.org/10.1016/S0009-2509(98)00489-8	journal	July 1999
First-principles-based molecular simulation of heterogeneous catalytic surface chemistry Neurock, Matthew; Hansen, Eric W. Computers & Chemical Engineering, Vol. 22 https://doi.org/10.1016/S0098-1354(98)00210-5	journal	March 1998
Coupled theoretical and experimental analysis of surface coverage effects in Pt-catalyzed NO and O2 reaction to NO2 on Pt(111) Smeltz, A. D.; Getman, R. B.; Schneider, W. F. Catalysis Today, Vol. 136, Issue 1-2 https://doi.org/10.1016/j.cattod.2007.12.139	journal	July 2008
The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis Bligaard, T.; Nørskov, J. K.; Dahl, S. Journal of Catalysis, Vol. 224, Issue 1 https://doi.org/10.1016/j.jcat.2004.02.034	journal	May 2004
First-principles-based kinetic Monte Carlo simulation of the selective hydrogenation of acetylene over Pd(111) Mei, D.; Sheth, P.; Neurock, M. Journal of Catalysis, Vol. 242, Issue 1 https://doi.org/10.1016/j.jcat.2006.05.009	journal	August 2006
Reaction of NO and O2 to NO2 on Pt: Kinetics and catalyst deactivation Mulla, S.; Chen, N.; Cumaranatunge, L. Journal of Catalysis, Vol. 241, Issue 2 https://doi.org/10.1016/j.jcat.2006.05.016	journal	July 2006
Effect of multiscale model uncertainty on identification of optimal catalyst properties Ulissi, Z.; Prasad, V.; Vlachos, D. G. Journal of Catalysis, Vol. 281, Issue 2 https://doi.org/10.1016/j.jcat.2011.05.019	journal	July 2011
Accurate coverage-dependence incorporated into first-principles kinetic models: Catalytic NO oxidation on Pt (111) Wu, C.; Schmidt, D. J.; Wolverton, C. Journal of Catalysis, Vol. 286 https://doi.org/10.1016/j.jcat.2011.10.020	journal	February 2012
On the effect of coverage-dependent adsorbate–adsorbate interactions for CO methanation on transition metal surfaces Lausche, Adam C.; Medford, Andrew J.; Khan, Tuhin Suvra Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.08.002	journal	November 2013
Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (100) surfaces Liu, Da-Jiang; Evans, James W. Progress in Surface Science, Vol. 88, Issue 4 https://doi.org/10.1016/j.progsurf.2013.10.001	journal	December 2013
Quasi-chemical approximation for polyatomics: Statistical thermodynamics of adsorption Dávila, M.; Romá, F.; Riccardo, J. L. Surface Science, Vol. 600, Issue 10 https://doi.org/10.1016/j.susc.2006.02.032	journal	May 2006
First-principles reaction site model for coverage-sensitive surface reactions: Pt(111)–O temperature programmed desorption Bray, J. M.; Skavdahl, I. J.; McEwen, J. -S. Surface Science, Vol. 622 https://doi.org/10.1016/j.susc.2013.12.005	journal	April 2014
Framework for Scalable Adsorbate–Adsorbate Interaction Models Hoffmann, Max J.; Medford, Andrew J.; Bligaard, Thomas The Journal of Physical Chemistry C, Vol. 120, Issue 24 https://doi.org/10.1021/acs.jpcc.6b03375	journal	June 2016
Adsorbate Entropies with Complete Potential Energy Sampling in Microkinetic Modeling Jørgensen, Mikkel; Grönbeck, Henrik The Journal of Physical Chemistry C, Vol. 121, Issue 13 https://doi.org/10.1021/acs.jpcc.6b11487	journal	March 2017
Quantitative Studies of the Coverage Effects on Microkinetic Simulations for NO Oxidation on Pt(111) Ding, Yunxuan; Xu, Yarong; Song, Yihui The Journal of Physical Chemistry C, Vol. 123, Issue 45 https://doi.org/10.1021/acs.jpcc.9b08208	journal	October 2019
Volcano Curves for in Silico Prediction of Mono- and Bifunctional Catalysts: Application to Ammonia Decomposition Wu, Hongbo; Sutton, Jonathan E.; Guo, Wei The Journal of Physical Chemistry C, Vol. 123, Issue 44 https://doi.org/10.1021/acs.jpcc.9b08662	journal	October 2019
Comparison of Coverage-Dependent Binding Energy Models for Mean-Field Microkinetic Rate Predictions Bajpai, Anshumaan; Frey, Kurt; Schneider, William F. Langmuir, Vol. 36, Issue 1 https://doi.org/10.1021/acs.langmuir.9b03563	journal	December 2019
Kinetic Monte Carlo Modeling for the NO–CO Reaction Mechanism on Rh(100) and Rh(111) Liu, Jiangyue; Tan, Lu; Huang, Liangliang Langmuir, Vol. 36, Issue 12 https://doi.org/10.1021/acs.langmuir.9b03720	journal	February 2020
Plasma-Catalytic Ammonia Synthesis beyond the Equilibrium Limit Mehta, Prateek; Barboun, Patrick M.; Engelmann, Yannick ACS Catalysis, Vol. 10, Issue 12 https://doi.org/10.1021/acscatal.0c00684	journal	May 2020
Benchmark First-Principles Calculations of Adsorbate Free Energies Bajpai, Anshumaan; Mehta, Prateek; Frey, Kurt ACS Catalysis, Vol. 8, Issue 3 https://doi.org/10.1021/acscatal.7b03438	journal	January 2018
Electrons to Reactors Multiscale Modeling: Catalytic CO Oxidation over RuO ₂ Sutton, Jonathan E.; Lorenzi, Juan M.; Krogel, Jaron T. ACS Catalysis, Vol. 8, Issue 6 https://doi.org/10.1021/acscatal.8b00713	journal	April 2018
Beyond Mean-Field Microkinetics: Toward Accurate and Efficient Theoretical Modeling in Heterogeneous Catalysis Chen, Zheng; Wang, He; Su, Neil Qiang ACS Catalysis, Vol. 8, Issue 7 https://doi.org/10.1021/acscatal.8b00943	journal	April 2018
Progress in Accurate Chemical Kinetic Modeling, Simulations, and Parameter Estimation for Heterogeneous Catalysis Matera, Sebastian; Schneider, William F.; Heyden, Andreas ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b01234	journal	June 2019
CO Oxidation on Pd(111): A First-Principles-Based Kinetic Monte Carlo Study Piccinin, Simone; Stamatakis, Michail ACS Catalysis, Vol. 4, Issue 7 https://doi.org/10.1021/cs500377j	journal	May 2014
First-Principles Analysis of Structure Sensitivity in NO Oxidation on Pt Bray, J. M.; Schneider, W. F. ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501783q	journal	January 2015
Performance of Cluster Expansions of Coverage-Dependent Adsorption of Atomic Oxygen on Pt(111) Schmidt, David J.; Chen, Wei; Wolverton, C. Journal of Chemical Theory and Computation, Vol. 8, Issue 1 https://doi.org/10.1021/ct200659c	journal	December 2011
Thermodynamic Consistency in Microkinetic Development of Surface Reaction Mechanisms Mhadeshwar, A. B.; Wang, H.; Vlachos, D. G. The Journal of Physical Chemistry B, Vol. 107, Issue 46 https://doi.org/10.1021/jp034954y	journal	November 2003
First-Principles-Based Kinetic Monte Carlo Simulation of the Structure Sensitivity of the Water–Gas Shift Reaction on Platinum Surfaces Stamatakis, Michail; Chen, Ying; Vlachos, Dionisios G. The Journal of Physical Chemistry C, Vol. 115, Issue 50 https://doi.org/10.1021/jp2071869	journal	November 2011
Mechanism of the Water Gas Shift Reaction on Pt: First Principles, Experiments, and Microkinetic Modeling Grabow, Lars C.; Gokhale, Amit A.; Evans, Steven T. The Journal of Physical Chemistry C, Vol. 112, Issue 12 https://doi.org/10.1021/jp7099702	journal	March 2008
Thermodynamics of Environment-Dependent Oxygen Chemisorption on Pt(111) Getman, Rachel B.; Xu, Ye; Schneider, William F. The Journal of Physical Chemistry C, Vol. 112, Issue 26 https://doi.org/10.1021/jp800905a	journal	June 2008
Coverage-Dependent CO Adsorption Energy from First-Principles Calculations Shan, Bin; Zhao, Yujun; Hyun, Jangsuk The Journal of Physical Chemistry C, Vol. 113, Issue 15 https://doi.org/10.1021/jp8094962	journal	March 2009
Oxidation of NO with O ₂ on Pt(111) and Pt(321) Large Single Crystals ^† Smeltz, Andrew D.; Delgass, W. Nicholas; Ribeiro, Fabio H. Langmuir, Vol. 26, Issue 21 https://doi.org/10.1021/la101653x	journal	November 2010
Implications of coverage-dependent O adsorption for catalytic NO oxidation on the late transition metals Frey, Kurt; Schmidt, David J.; Wolverton, C. Catal. Sci. Technol., Vol. 4, Issue 12 https://doi.org/10.1039/C4CY00763H	journal	January 2014
A new insight into the initial step in the Fischer–Tropsch synthesis: CO dissociation on Ru surfaces Li, Hongping; Fu, Gang; Xu, Xin Physical Chemistry Chemical Physics, Vol. 14, Issue 48 https://doi.org/10.1039/c2cp43176a	journal	January 2012
Including lateral interactions into microkinetic models of catalytic reactions Hellman, A.; Honkala, K. The Journal of Chemical Physics, Vol. 127, Issue 19 https://doi.org/10.1063/1.2790885	journal	November 2007
A graph-theoretical kinetic Monte Carlo framework for on-lattice chemical kinetics Stamatakis, Michail; Vlachos, Dionisios G. The Journal of Chemical Physics, Vol. 134, Issue 21 https://doi.org/10.1063/1.3596751	journal	June 2011
On the effects of adsorbate aggregation on the kinetics of surface reactions Silverberg, M.; Ben‐Shaul, A.; Rebentrost, F. The Journal of Chemical Physics, Vol. 83, Issue 12 https://doi.org/10.1063/1.449550	journal	December 1985
Adsorbate islanding in surface reactions: A combined Monte Carlo‐lattice gas approach Silverberg, M.; Ben‐Shaul, A. The Journal of Chemical Physics, Vol. 87, Issue 5 https://doi.org/10.1063/1.453005	journal	September 1987
Adsorption kinetics of chemisorption by surface abstraction and dissociative adsorption Sholl, David S. The Journal of Chemical Physics, Vol. 106, Issue 1 https://doi.org/10.1063/1.473194	journal	January 1997
Parallel kinetic Monte Carlo simulation framework incorporating accurate models of adsorbate lateral interactions Nielsen, Jens; d’Avezac, Mayeul; Hetherington, James The Journal of Chemical Physics, Vol. 139, Issue 22 https://doi.org/10.1063/1.4840395	journal	December 2013
Structure sensitivity in oxide catalysis: First-principles kinetic Monte Carlo simulations for CO oxidation at RuO ₂ (111) Wang, Tongyu; Reuter, Karsten The Journal of Chemical Physics, Vol. 143, Issue 20 https://doi.org/10.1063/1.4936354	journal	November 2015
A machine learning approach to graph-theoretical cluster expansions of the energy of adsorbate layers Vignola, Emanuele; Steinmann, Stephan N.; Vandegehuchte, Bart D. The Journal of Chemical Physics, Vol. 147, Issue 5 https://doi.org/10.1063/1.4985890	journal	August 2017
Beyond mean-field approximations for accurate and computationally efficient models of on-lattice chemical kinetics Pineda, M.; Stamatakis, M. The Journal of Chemical Physics, Vol. 147, Issue 2 https://doi.org/10.1063/1.4991690	journal	July 2017
Adlayer structure and lattice size effects on catalytic rates predicted from KMC simulations: NO oxidation on Pt(111) Papanikolaou, Konstantinos G.; Darby, Matthew T.; Stamatakis, Michail The Journal of Chemical Physics, Vol. 149, Issue 18 https://doi.org/10.1063/1.5048787	journal	November 2018
Kinetic description of site ensembles on catalytic surfaces Razdan, Neil K.; Bhan, Aditya Proceedings of the National Academy of Sciences, Vol. 118, Issue 8 https://doi.org/10.1073/pnas.2019055118	journal	February 2021
Uncertainty and figure selection for DFT based cluster expansions for oxygen adsorption on Au and Pt (111) surfaces Miller, Spencer D.; Kitchin, John R. Molecular Simulation, Vol. 35, Issue 10-11 https://doi.org/10.1080/08927020902833137	journal	August 2009
Kinetic modelling of heterogeneous catalytic systems Stamatakis, Michail Journal of Physics: Condensed Matter, Vol. 27, Issue 1 https://doi.org/10.1088/0953-8984/27/1/013001	journal	November 2014
Coverage dependence of N 2 dissociation at an N, O, or H precovered Ru(0001) surface investigated with density functional theory Hammer, B. Physical Review B, Vol. 63, Issue 20 https://doi.org/10.1103/PhysRevB.63.205423	journal	May 2001
Phase diagram of oxygen adsorbed on platinum (111) by first-principles investigation Tang, Hairong; Van der Ven, Anton; Trout, Bernhardt L. Physical Review B, Vol. 70, Issue 4 https://doi.org/10.1103/PhysRevB.70.045420	journal	July 2004
NO oxidation properties of Pt(111) revealed by ab initio kinetic simulations Ovesson, S.; Lundqvist, B. I.; Schneider, W. F. Physical Review B, Vol. 71, Issue 11 https://doi.org/10.1103/PhysRevB.71.115406	journal	March 2005
First-principles kinetic Monte Carlo simulations for heterogeneous catalysis: Application to the CO oxidation at Ru O 2 ( 110 ) Reuter, Karsten; Scheffler, Matthias Physical Review B, Vol. 73, Issue 4 https://doi.org/10.1103/PhysRevB.73.045433	journal	January 2006
CO oxidation on Pd(100) at technologically relevant pressure conditions: First-principles kinetic Monte Carlo study Rogal, Jutta; Reuter, Karsten; Scheffler, Matthias Physical Review B, Vol. 77, Issue 15 https://doi.org/10.1103/PhysRevB.77.155410	journal	April 2008
Density functional theory study of the initial oxidation of the Pt(111) surface Hawkins, Jeffery M.; Weaver, Jason F.; Asthagiri, Aravind Physical Review B, Vol. 79, Issue 12 https://doi.org/10.1103/PhysRevB.79.125434	journal	March 2009
Correlations in coverage-dependent atomic adsorption energies on Pd(111) Kitchin, John R. Physical Review B, Vol. 79, Issue 20 https://doi.org/10.1103/PhysRevB.79.205412	journal	May 2009
A Practical Guide to Surface Kinetic Monte Carlo Simulations Andersen, Mie; Panosetti, Chiara; Reuter, Karsten Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00202	journal	April 2019
Micro-Kinetic Modelling of CO-TPD from Fe(100)—Incorporating Lateral Interactions Gambu, Thobani; Abrahams, R.; van Steen, Eric Catalysts, Vol. 9, Issue 4 https://doi.org/10.3390/catal9040310	journal	March 2019

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Title: Consequences of adsorbate-adsorbate interactions for apparent kinetics of surface catalytic reactions

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