Incorporating Coverage-Dependent Reaction Barriers into First-Principles-Based Microkinetic Models: Approaches and Challenges

Nolen, Michelle A.; Farberow, Carrie A.; Kwon, Stephanie

doi:10.1021/acscatal.4c03358

Incorporating Coverage-Dependent Reaction Barriers into First-Principles-Based Microkinetic Models: Approaches and Challenges

Journal Article · Wed Sep 11 00:00:00 EDT 2024 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.4c03358· OSTI ID:2447846

Nolen, Michelle A. ^[1]; Farberow, Carrie A. ^[2]; ^[3]

National Renewable Energy Laboratory (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Colorado School of Mines, Golden, CO (United States)

Mean-field microkinetic models (MKMs) are appealing for their relatively facile construction, computational tractability, and high-throughput catalyst screening capabilities. As such, they will continue to be a valuable tool for materials design in heterogeneous catalysis even as the field aims to describe more complex systems. Numerous prior reports have provided the groundwork for constructing first-principles-based MKMs, including the analysis of strategies for incorporating lateral interactions into thermodynamic parameters (e.g., adsorption energies). Yet, there remains a need for concerted dialogue on methods for calculating and incorporating coverage-dependent kinetic parameters into MKMs. In this Perspective, we assess strategies for doing so, including the corresponding key physical implications and computational challenges. Here, we emphasize that decoupling thermodynamic and kinetic parameters within MKMs can violate thermodynamic consistency and risk unphysical solutions. For some reactions and catalyst materials, scaling relationships can predict coverage-dependent activation energies, but there are several exceptions evident in the literature, indicating that this approach is not universally applicable and that the field could benefit from research aimed at elucidating the limitations. Conducting high-coverage transition state searches is a rigorous but computationally costly strategy, and the effects of various methods for mitigating this cost on resulting energetics have yet to be broadly explored and validated. The goal of this Perspective is to generate discussion on and inspire focused research into the physical relevance of approaches for describing coverage-dependent reaction barriers in MKMs, including the development of computationally tractable methodologies, to advance the applicability of MKMs across diverse reaction chemistries and conditions.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 2447846

Report Number(s):: NREL/JA--5100-91094; MainId:92872; UUID:8659f421-900a-46b3-a730-c51d3f0b2537; MainAdminId:73873

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 18 Vol. 14; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

Mechanistic Role of Water on the Rate and Selectivity of Fischer-Tropsch Synthesis on Ruthenium Catalysts Hibbitts, David D.; Loveless, Brett T.; Neurock, Matthew Angewandte Chemie International Edition, Vol. 52, Issue 47 https://doi.org/10.1002/anie.201304610	journal	October 2013
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
First-Principles-Based Monte Carlo Simulation of Ethylene Hydrogenation Kinetics on Pd Hansen, Eric W.; Neurock, Matthew Journal of Catalysis, Vol. 196, Issue 2 https://doi.org/10.1006/jcat.2000.3018	journal	December 2000
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
Universal Brønsted-Evans-Polanyi Relations for C–C, C–O, C–N, N–O, N–N, and O–O Dissociation Reactions Wang, Shengguang; Temel, Burcin; Shen, Juan Catalysis Letters, Vol. 141, Issue 3 https://doi.org/10.1007/s10562-010-0477-y	journal	November 2010
CatMAP: A Software Package for Descriptor-Based Microkinetic Mapping of Catalytic Trends Medford, Andrew J.; Shi, Chuan; Hoffmann, Max J. Catalysis Letters, Vol. 145, Issue 3 https://doi.org/10.1007/s10562-015-1495-6	journal	February 2015
Extracting meaningful standard enthalpies and entropies of activation for surface reactions from kinetic rates Doyle, Peter J.; Savara, Aditya; Raiman, Stephen S. Reaction Kinetics, Mechanisms and Catalysis, Vol. 129, Issue 2 https://doi.org/10.1007/s11144-020-01747-2	journal	March 2020
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
The effect of adsorbate-induced surface reconstruction on the apparent arrhenius parameters for desorption Zhdanov, V. P. Progress in Surface Science, Vol. 35, Issue 1-4 https://doi.org/10.1016/0079-6816(90)90032-F	journal	January 1990
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
Evaluating the benefits of kinetic Monte Carlo and microkinetic modeling for catalyst design studies in the presence of lateral interactions Li, Xiao; Grabow, Lars C. Catalysis Today, Vol. 387 https://doi.org/10.1016/j.cattod.2021.03.010	journal	March 2022
Machine learning of lateral adsorbate interactions in surface reaction kinetics Mou, Tianyou; Han, Xue; Zhu, Huiyuan Current Opinion in Chemical Engineering, Vol. 36 https://doi.org/10.1016/j.coche.2022.100825	journal	June 2022
Microkinetic analysis and mechanism of the water gas shift reaction over copper catalysts Madon, Rostam J.; Braden, Drew; Kandoi, Shampa Journal of Catalysis, Vol. 281, Issue 1 https://doi.org/10.1016/j.jcat.2011.03.008	journal	July 2011
Adsorbate interactions on surface lead to a flattened Sabatier volcano plot in reduction of oxygen Qi, Liang; Li, Ju Journal of Catalysis, Vol. 295 https://doi.org/10.1016/j.jcat.2012.07.019	journal	November 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
DFT-driven multi-site microkinetic modeling of ethanol conversion to ethylene and diethyl ether on γ-Al2O3(1 1 1) Christiansen, Matthew A.; Mpourmpakis, Giannis; Vlachos, Dionisios G. Journal of Catalysis, Vol. 323 https://doi.org/10.1016/j.jcat.2014.12.024	journal	March 2015
Reactivity and selectivity descriptors of dioxygen activation routes on metal oxides Kwon, Stephanie; Deshlahra, Prashant; Iglesia, Enrique Journal of Catalysis, Vol. 377 https://doi.org/10.1016/j.jcat.2019.07.048	journal	September 2019
Unimolecular and bimolecular formic acid decomposition routes on dispersed Cu nanoparticles Lin, Ting Chun; De La Torre, Unai; Hejazi, Ava Journal of Catalysis, Vol. 404 https://doi.org/10.1016/j.jcat.2021.08.049	journal	December 2021
Catalytic site ensembles: A context to reexamine the Langmuir-Hinshelwood kinetic description Razdan, N. K.; Bhan, A. Journal of Catalysis, Vol. 404 https://doi.org/10.1016/j.jcat.2021.09.016	journal	December 2021
Consequences of adsorbate-adsorbate interactions for apparent kinetics of surface catalytic reactions Goswami, Anshuman; Ma, Hanyu; Schneider, William F. Journal of Catalysis, Vol. 405 https://doi.org/10.1016/j.jcat.2021.12.005	journal	January 2022
Mean field model parameterization to recover coverage-dependent kinetics Goswami, Anshuman; Schneider, William F. Journal of Catalysis, Vol. 426 https://doi.org/10.1016/j.jcat.2023.07.013	journal	October 2023
A cluster expansion model for predicting activation barrier of atomic processes Rehman, Tafizur; Jaipal, M.; Chatterjee, Abhijit Journal of Computational Physics, Vol. 243 https://doi.org/10.1016/j.jcp.2013.03.005	journal	June 2013
A cluster expansion model for rate constants of surface diffusion processes on Ag, Al, Cu, Ni, Pd and Pt(100) surfaces Verma, Sumit; Rehman, Tafizur; Chatterjee, Abhijit Surface Science, Vol. 613 https://doi.org/10.1016/j.susc.2013.03.022	journal	July 2013
On the structure sensitivity of and CO coverage effects on formic acid decomposition on Pd surfaces Li, Sha; Rangarajan, Srinivas; Scaranto, Jessica Surface Science, Vol. 709 https://doi.org/10.1016/j.susc.2021.121846	journal	July 2021
Combining Computational Modeling with Reaction Kinetics Experiments for Elucidating the In Situ Nature of the Active Site in Catalysis Bhandari, Saurabh; Rangarajan, Srinivas; Mavrikakis, Manos Accounts of Chemical Research, Vol. 53, Issue 9 https://doi.org/10.1021/acs.accounts.0c00340	journal	September 2020
Achieving Theory–Experiment Parity for Activity and Selectivity in Heterogeneous Catalysis Using Microkinetic Modeling Xie, Wenbo; Xu, Jiayan; Chen, Jianfu Accounts of Chemical Research, Vol. 55, Issue 9, p. 1237-1248 https://doi.org/10.1021/acs.accounts.2c00058	journal	April 2022
Prevalence of Bimolecular Routes in the Activation of Diatomic Molecules with Strong Chemical Bonds (O ₂ , NO, CO, N ₂ ) on Catalytic Surfaces Hibbitts, David; Iglesia, Enrique Accounts of Chemical Research, Vol. 48, Issue 5 https://doi.org/10.1021/acs.accounts.5b00063	journal	April 2015
Microkinetic Modeling: A Tool for Rational Catalyst Design Motagamwala, Ali Hussain; Dumesic, James A. Chemical Reviews, Vol. 121, Issue 2 https://doi.org/10.1021/acs.chemrev.0c00394	journal	November 2020
Computational Methods in Heterogeneous Catalysis Chen, Benjamin W. J.; Xu, Lang; Mavrikakis, Manos Chemical Reviews, Vol. 121, Issue 2 https://doi.org/10.1021/acs.chemrev.0c01060	journal	December 2020
Machine-Learned Corrections to Mean-Field Microkinetic Models at the Fast Diffusion Limit Tian, Huijie; Rangarajan, Srinivas The Journal of Physical Chemistry C, Vol. 125, Issue 37 https://doi.org/10.1021/acs.jpcc.1c04495	journal	September 2021
Equilibrium Constants and Rate Constants for Adsorbates: Two-Dimensional (2D) Ideal Gas, 2D Ideal Lattice Gas, and Ideal Hindered Translator Models Campbell, Charles T.; Sprowl, Lynza H.; Árnadóttir, Líney The Journal of Physical Chemistry C, Vol. 120, Issue 19 https://doi.org/10.1021/acs.jpcc.6b00975	journal	May 2016
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
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
Quantitative Insights into the Reaction Mechanism for the Direct Synthesis of H₂O₂ over Transition Metals: Coverage-Dependent Microkinetic Modeling Yao, Zihao; Zhao, Jinyan; Bunting, Rhys J. ACS Catalysis, Vol. 11, Issue 3 https://doi.org/10.1021/acscatal.0c04125	journal	January 2021
Role of Hydrogen-bonded Bimolecular Formic Acid–Formate Complexes for Formic Acid Decomposition on Copper: A Combined First-Principles and Microkinetic Modeling Study Chen, Benjamin W. J.; Bhandari, Saurabh; Mavrikakis, Manos ACS Catalysis, Vol. 11, Issue 7 https://doi.org/10.1021/acscatal.0c05695	journal	March 2021
Coverage-Dependent Microkinetics in Heterogeneous Catalysis Powered by the Maximum Rate Analysis Chen, Zheng; Liu, Zhangyun; Xu, Xin ACS Catalysis, Vol. 11, Issue 15, p. 9333-9344 https://doi.org/10.1021/acscatal.1c01997	journal	July 2021
Microkinetic Modeling of Propene Combustion on a Stepped, Metallic Palladium Surface and the Importance of Oxygen Coverage Streibel, Verena; Aljama, Hassan A.; Yang, An-Chih ACS Catalysis, Vol. 12, Issue 3 https://doi.org/10.1021/acscatal.1c03699	journal	January 2022
Selectivity Trends and Role of Adsorbate–Adsorbate Interactions in CO Hydrogenation on Rhodium Catalysts Deimel, Martin; Prats, Hector; Seibt, Michael ACS Catalysis, Vol. 12, Issue 13 https://doi.org/10.1021/acscatal.2c02353	journal	June 2022
Significance of Surface Formate Coverage on the Reaction Kinetics of Methanol Synthesis from CO 2 Hydrogenation over Cu Wu, Panpan; Yang, Bo ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b01910	journal	September 2017
CO Adsorption on Pt(111): From Isolated Molecules to Ordered High-Coverage Structures Gunasooriya, G. T. Kasun Kalhara; Saeys, Mark ACS Catalysis, Vol. 8, Issue 11 https://doi.org/10.1021/acscatal.8b02371	journal	September 2018
Quantitative Determination of C–C Coupling Mechanisms and Detailed Analyses on the Activity and Selectivity for Fischer–Tropsch Synthesis on Co(0001): Microkinetic Modeling with Coverage Effects Yao, Zihao; Guo, Chenxi; Mao, Yu ACS Catalysis, Vol. 9, Issue 7 https://doi.org/10.1021/acscatal.9b01150	journal	May 2019
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
Kinetic Isolation between Turnovers on Au ₁₈ Nanoclusters: Formic Acid Decomposition One Molecule at a Time Chen, Benjamin W. J.; Stamatakis, Michail; Mavrikakis, Manos ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b02167	journal	September 2019
Reaction Mechanism of Vapor-Phase Formic Acid Decomposition over Platinum Catalysts: DFT, Reaction Kinetics Experiments, and Microkinetic Modeling Bhandari, Saurabh; Rangarajan, Srinivas; Maravelias, Christos T. ACS Catalysis, Vol. 10, Issue 7 https://doi.org/10.1021/acscatal.9b05424	journal	March 2020
Reactivity Theory of Transition-Metal Surfaces: A Brønsted−Evans−Polanyi Linear Activation Energy−Free-Energy Analysis van Santen, Rutger A.; Neurock, Matthew; Shetty, Sharan G. Chemical Reviews, Vol. 110, Issue 4 https://doi.org/10.1021/cr9001808	journal	December 2009
A Theoretical and Computational Analysis of Linear Free Energy Relations for the Estimation of Activation Energies Sutton, Jonathan E.; Vlachos, Dionisios G. ACS Catalysis, Vol. 2, Issue 8 https://doi.org/10.1021/cs3003269	journal	July 2012
Density Functional Theory Calculations and Analysis of Reaction Pathways for Reduction of Nitric Oxide by Hydrogen on Pt(111) Farberow, Carrie A.; Dumesic, James A.; Mavrikakis, Manos ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs500668k	journal	September 2014
A Correlation of Reaction Rates Hammond, George S. Journal of the American Chemical Society, Vol. 77, Issue 2 https://doi.org/10.1021/ja01607a027	journal	January 1955
Chemisorption of CO and Mechanism of CO Oxidation on Supported Platinum Nanoclusters Allian, Ayman D.; Takanabe, Kazuhiro; Fujdala, Kyle L. Journal of the American Chemical Society, Vol. 133, Issue 12 https://doi.org/10.1021/ja110073u	journal	March 2011
CO Chemisorption and Dissociation at High Coverages during CO Hydrogenation on Ru Catalysts Loveless, Brett T.; Buda, Corneliu; Neurock, Matthew Journal of the American Chemical Society, Vol. 135, Issue 16 https://doi.org/10.1021/ja311848e	journal	April 2013
Dense CO Adlayers as Enablers of CO Hydrogenation Turnovers on Ru Surfaces Liu, Jianwei; Hibbitts, David; Iglesia, Enrique Journal of the American Chemical Society, Vol. 139, Issue 34 https://doi.org/10.1021/jacs.7b04606	journal	August 2017
Standard States for Adsorption on Solid Surfaces: 2D Gases, Surface Liquids, and Langmuir Adsorbates Savara, Aditya The Journal of Physical Chemistry C, Vol. 117, Issue 30 https://doi.org/10.1021/jp404398z	journal	July 2013
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
Harmonic Vibrational Frequencies: An Evaluation of Hartree−Fock, Møller−Plesset, Quadratic Configuration Interaction, Density Functional Theory, and Semiempirical Scale Factors Scott, Anthony P.; Radom, Leo The Journal of Physical Chemistry, Vol. 100, Issue 41 https://doi.org/10.1021/jp960976r	journal	January 1996
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
How coverage influences thermodynamic and kinetic isotope effects for H ₂ /D ₂ dissociative adsorption on transition metals Chen, Benjamin W. J.; Mavrikakis, Manos Catalysis Science & Technology, Vol. 10, Issue 3 https://doi.org/10.1039/C9CY02338K	journal	January 2020
The Activated Complex in Chemical Reactions Eyring, Henry The Journal of Chemical Physics, Vol. 3, Issue 2 https://doi.org/10.1063/1.1749604	journal	February 1935
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
Perspective: Methods for large-scale density functional calculations on metallic systems Aarons, Jolyon; Sarwar, Misbah; Thompsett, David The Journal of Chemical Physics, Vol. 145, Issue 22 https://doi.org/10.1063/1.4972007	journal	December 2016
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
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

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Incorporating Coverage-Dependent Reaction Barriers into First-Principles-Based Microkinetic Models: Approaches and Challenges

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