Abstract
Microkinetic modeling (MKM) breaks down a reaction mechanism into all known elementary steps making no a priori assumptions about dominant reaction paths, rate determining steps, and most abundant reactive intermediates. Instead this information emerges from the solution of the model. Aside from mechanistic understanding, MKM can be utilized to optimize reaction conditions and/or reactor configuration and provide guidelines for catalyst design. This chapter focuses on describing the basics of mean-field MKM. It also details how first-principles calculations or fast-screening methods can be used in conjunction with transition state theory and statistical mechanics to derive kinetic and thermodynamic parameters that abide to thermodynamic consistency constraints. Finally, the chapter covers analysis techniques that provide key insights into the reaction mechanism. We focus primarily on the ammonia decomposition chemistry as an illustrative example.
References
Abild-Pedersen F, Greeley J, Studt F et al (2007) Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces. Phys Rev Lett 99:4–7. https://doi.org/10.1103/PhysRevLett.99.016105
Aghalayam P, Park YK, Vlachos DG (2000) Construction and optimization of complex surface-reaction mechanisms. AICHE J 46:2017–2029. https://doi.org/10.1002/aic.690461013
Coltrin ME, Kee RJ, Rupley FM (1996) Surface Chemkin-III: a Fortran package for analyzing heterogeneous chemical kinetics at a solid-surface – gas-phase interface. Sandia National Laboratory, Albuquerque, NM
Cornish-Bowden A (2015) One hundred years of Michaelis–Menten kinetics. Perspect Sci 4:3–9. https://doi.org/10.1016/j.pisc.2014.12.002
Deshmukh SR, Vlachos DG (2007) A reduced mechanism for methane and one-step rate expressions for fuel-lean catalytic combustion of small alkanes on noble metals. Combust Flame 149:366–383. https://doi.org/10.1016/j.combustflame.2007.02.006
Dumesic JA, Rudd DF (1993) The microkinetics of heterogeneous catalysis. American Chemical Society, Washington, DC
Falsig H, Shen J, Khan TS et al (2014) On the structure sensitivity of direct NO decomposition over low-index transition metal facets. Top Catal 57:80–88. https://doi.org/10.1007/s11244-013-0164-5
Fernndez EM, Moses PG, Toftelund A et al (2008) Scaling relationships for adsorption energies on transition metal oxide, sulfide, and nitride surfaces. Angew Chem Int Ed 47:4683–4686. https://doi.org/10.1002/anie.200705739
Guo W, Vlachos DG (2013) Effect of local metal microstructure on adsorption on bimetallic surfaces: atomic nitrogen on Ni/Pt (111). J Chem Phys 174702:2–4. https://doi.org/10.1063/1.4803128
Guo W, Vlachos DG (2015a) Patched bimetallic surfaces are active catalysts for ammonia decomposition. Nat Commun 6:1–7. https://doi.org/10.1038/ncomms9619
Guo W, Vlachos DG (2015b) Patched bimetallic surfaces are active catalysts for ammonia decomposition: supplementary info. Nat Commun 6:1–7
Hill TL (1962) An introduction to statistical thermodynamics. Dover Publications, New York
Jones G, Bligaard T, Abild-Pedersen F, Nørskov JK (2008) Using scaling relations to understand trends in the catalytic activity of transition metals. J Phys Condens Matter 20:064239. https://doi.org/10.1088/0953-8984/20/6/064239
Laidler K, King M (1983) The development of transition-state theory. J Phys Chem 87:2657–2664
Lund EW (1965) Guldberg and Waage and the law of mass action. J Chem Educ 42:548. https://doi.org/10.1021/ed042p548
Mhadeshwar AB, Vlachos DG (2004) Microkinetic modeling for water-promoted CO oxidation, water-gas shift, and preferential oxidation of CO on Pt. J Phys Chem B 108:15246–15258. https://doi.org/10.1021/jp048698g
Mhadeshwar AB, Wang H, Vlachos DG (2003) Thermodynamic consistency in microkinetic development of surface reaction mechanisms. J Phys Chem B 107:12721–12733. https://doi.org/10.1021/jp034954y
Mhadeshwar AB, Kitchin JR, Barteau MA, Vlachos DG (2004) The role of adsorbate – adsorbate interactions in the rate controlling step and the most abundant reaction intermediate of NH3 decomposition on Ru. Catal Lett 96:13–22. https://doi.org/10.1023/B:CATL.0000029523.22277.e1
Motz H, Wise H (1960) Diffusion and heterogeneous reaction. III. Atom recombination at a catalytic boundary. J Chem Phys 32:1893–1894. https://doi.org/10.1063/1.1731060
Nicolaides A, Rauk A, Glukhovtsev MN, Radom L (1996) Heats of formation from G2, G2(MP2), and G2(MP2,SVP) total energies. J Phys Chem 100:17460–17464. https://doi.org/10.1021/jp9613753
Nørskov JK (1993) Adsorbate-adsorbate interactions on metal surfaces, Chapter 1. In: King DA, Woodruff DP (eds) Coadsorption, promoters and poisons. Elsevier, Amsterdam, pp 1–27
Park YK, Aghalayam P, Vlachos DG (1999) A generalized approach for predicting coverage-dependent reaction parameters of complex surface reactions: application to H2 oxidation over platinum. J Phys Chem A 103:8101–8107. https://doi.org/10.1021/jp9916485
Raimondeau S, Vlachos DG (2003) Front propagation at low temperatures and multiscale modeling for the catalytic combustion of H2 on Pt. Chem Eng Sci 58:657–663. https://doi.org/10.1016/S0009-2509(02)00592-4
Reuter K, Scheffler M (2001) Composition, structure, and stability of RuO2(110) as a function of oxygen pressure. Phys Rev B 65:35406. https://doi.org/10.1103/PhysRevB.65.035406
Salciccioli M, Stamatakis M, Caratzoulas S, Vlachos DG (2011) A review of multiscale modeling of metal-catalyzed reactions: mechanism development for complexity and emergent behavior. Chem Eng Sci 66:4319–4355. https://doi.org/10.1016/j.ces.2011.05.050
Samant A, Vlachos DG (2005) Overcoming stiffness in stochastic simulation stemming from partial equilibrium: a multiscale Monte Carlo algorithm. J Chem Phys 123. https://doi.org/10.1063/1.2046628
Sandler SI (2010) An introduction to applied statistical thermodynamics, 1st edn. John Wiley & Sons, Hoboken, NJ, USA
Shustorovich E (1986) Chemisorption phenomena: analytic modeling based on perturbation theory and bond-order conservation. Surf Sci Rep 6:1–63. https://doi.org/10.1016/0167-5729(86)90003-8
Shustorovich E (1990) The bond-order conservation approach to chemisorption and heterogeneous catalysis: applications and implications. Adv Catal. https://doi.org/10.1016/S0360-0564(08)60364-8
Stamatakis M, Vlachos DG (2012) Unraveling the complexity of catalytic reactions via kinetic Monte Carlo simulation: current status and frontiers. ACS Catal 2:2648–2663. https://doi.org/10.1021/cs3005709
Stamatakis M, Chen Y, Vlachos DG (2011) First-principles-based kinetic Monte Carlo simulation of the structure sensitivity of the water-gas shift reaction on platinum surfaces. J Phys Chem C 115:24750–24762. https://doi.org/10.1021/jp2071869
Sutton JE, Vlachos DG (2012) A theoretical and computational analysis of linear free energy relations for the estimation of activation energies. ACS Catal 2:1624–1634. https://doi.org/10.1021/cs3003269
Sutton JE, Vlachos DG (2015) Building large microkinetic models with first-principles’ accuracy at reduced computational cost. Chem Eng Sci 121:190–199. https://doi.org/10.1016/j.ces.2014.09.011
van’t Hoff JH (1884) Études de dynamique chimique. Frederik Muller, Amsterdam. Google Books
Vojvodic A, James A, Studt F et al (2014) Exploring the limits: a low-pressure, low-temperature Haber – Bosch process: supplement. Chem Phys Lett 598:108–112. https://doi.org/10.1016/j.cplett.2014.03.003
Wijaya CD, Sumathi R, Green WH (2003) Thermodynamic properties and kinetic parameters for cyclic ether formation from hydroperoxyalkyl radicals. J Phys Chem A 107:4908–4920. https://doi.org/10.1021/jp027471n
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Section Editor information
Rights and permissions
Copyright information
© 2018 Springer International Publishing AG, part of Springer Nature
About this entry
Cite this entry
Wittreich, G.R., Alexopoulos, K., Vlachos, D.G. (2018). Microkinetic Modeling of Surface Catalysis. In: Andreoni, W., Yip, S. (eds) Handbook of Materials Modeling. Springer, Cham. https://doi.org/10.1007/978-3-319-50257-1_5-1
Download citation
DOI: https://doi.org/10.1007/978-3-319-50257-1_5-1
Received:
Accepted:
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-50257-1
Online ISBN: 978-3-319-50257-1
eBook Packages: Springer Reference Physics and AstronomyReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics