Abstract
While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed1. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C–H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.
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References
Horn, R. & Schlögl, R. Methane activation by heterogeneous catalysis. Catal. Lett. 145, 23–39 (2014).
Kumar, G., Lau, S. L. J., Krcha, M. D. & Janik, M. J. Correlation of methane activation and oxide catalyst reducibility and its implications for oxidative coupling. ACS Catal. 6, 1812–1821 (2016).
Wang, C. C., Siao, S. S. & Jiang, J. C–H bond activation of methane via σ–d interaction on the IrO2(110) surface: density functional theory study. J. Phys. Chem. C 116, 6367–6370 (2012).
Yoo, J. S., Khan, T. S., Abild-Pedersen, F., Nørskov, J. K. & Studt, F. On the role of the surface oxygen species during A–H (A = C, N, O) bond activation: a density functional theory study. Chem. Commun. 51, 2621–2624 (2015).
Weaver, J. F., Hakanoglu, C., Antony, A. & Asthagiri, A. Alkane activation on crystalline metal oxide surfaces. Chem. Soc. Rev. 43, 7536–7547 (2014).
Antony, A., Asthagiri, A. & Weaver, J. F. Pathways and kinetics of methane and ethane C–H bond cleavage on PdO(101). J. Chem. Phys. 139, 104702 (2013).
Abild-Pedersen, F. et al. Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces. Phys. Rev. Lett. 99, 016105 (2007).
Li, B. & Metiu, H. Dissociation of methane on La2O3 surfaces doped with Cu, Mg, or Zn. J. Phys. Chem. C 115, 18239–18246 (2011).
Krcha, M. D., Mayernick, A. D. & Janik, M. J. Periodic trends of oxygen vacancy formation and C–H bond activation over transition metal-doped CeO2 (111) surfaces. J. Catal. 293, 103–115 (2012).
Schwarz, H. Chemistry with methane: concepts rather than recipes. Angew. Chem. Int. Ed. 50, 10096–10115 (2011).
Woertink, J. S. et al. A [Cu2O]2+ core in Cu-ZSM-5, the active site in the oxidation of methane to methanol. Proc. Natl Acad. Sci. USA 106, 18908–18913 (2009).
Da Silva, J. C. S., Pennifold, R. C. R., Harvey, J. N. & Rocha, W. R. A radical rebound mechanism for the methane oxidation reaction promoted by the dicopper center of a pMMO enzyme: a computational perspective. Dalton Trans. 45, 2492–2504 (2016).
Chin, Y. H., Buda, C., Neurock, M. & Iglesia, E. Consequences of metal-oxide interconversion for C–H bond activation during CH4 reactions on Pd catalysts. J. Am. Chem. Soc. 135, 15425–15442 (2013).
Wulfers, M. J., Lobo, R. F., Ipek, B. & Teketel, S. Conversion of methane to methanol on copper-containing small-pore zeolites and zeotypes. Chem. Commun. 51, 4447–4450 (2015).
Hammond, C. et al. Direct catalytic conversion of methane to methanol in an aqueous medium by using copper-promoted Fe-ZSM-5. Angew. Chem. Int. Ed. 51, 5129–5133 (2012).
Grundner, S. et al. Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol. Nat. Commun. 6, 7546 (2015).
Groothaert, M. H., Smeets, P. J., Sels, B. F., Jacobs, P. A. & Schoonheydt, R. A. Selective oxidation of methane by the bis (μ-oxo) dicopper core stabilized on ZSM-5 and mordenite zeolites. J. Am. Chem. Soc. 127, 1394–1395 (2005).
Verma, P. et al. Mechanism of oxidation of ethane to ethanol at Iron(IV)-oxo sites in magnesium-diluted Fe2(dobdc). J. Am. Chem. Soc. 137, 5770–5781 (2015).
Xiao, D. J. et al. Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites. Nat. Chem. 6, 590–595 (2014).
Impeng, S. et al. Methane activation on Fe- and FeO-embedded graphene and boron nitride sheet: role of atomic defects in catalytic activities. RSC Adv. 5, 97918–97927 (2015).
Sun, X., Li, B. & Metiu, H. Methane dissociation on Li-, Na-, K-, and Cu-doped flat and stepped CaO(001). J. Phys. Chem. C 117, 7114–7122 (2013).
Lu, Y. et al. A high coking-resistance catalyst for methane aromatization. Chem. Commun. 2001, 2048–2049 (2001).
Tyo, E. C. et al. Oxidative dehydrogenation of cyclohexane on cobalt oxide (Co3O4) nanoparticles: the effect of particle size on activity and selectivity. ACS Catal. 2, 2409–2423 (2012).
Atzkern, S., Borisenko, S., Knupfer, M. & Golden, M. Valence-band excitations in V2O5 . Phys. Rev. B 5, 5849–5852 (2000).
Fu, G., Chen, Z. N., Xu, X. & Wan, H. L. Understanding the reactivity of the tetrahedrally coordinated high-valence d0 transition metal oxides toward the C–H bond activation of alkanes: a cluster model study. J. Phys. Chem. A 112, 717–721 (2008).
Chen, K., Xie, S., Bell, A. T. & Iglesia, E. Alkali effects on molybdenum oxide catalysts for the oxidative dehydrogenation of propane. J. Catal. 195, 244–252 (2000).
Tsai, C., Latimer, A. A., Yoo, J. S., Studt, F. & Abild-Pedersen, F. Predicting promoter-induced bond activation on solid catalysts using elementary bond orders. J. Phys. Chem. Lett. 6, 3670–3674 (2015).
Karp, E. M., Silbaugh, T. L. & Campbell, C. T. Bond energies of molecular fragments to metal surfaces track their bond energies to H atoms. J. Am. Chem. Soc. 136, 4137–4140 (2014).
Medford, A. J. et al. Assessing the reliability of calculated catalytic ammonia synthesis rates. Science 345, 197–200 (2014).
Wellendorff, J. et al. Density functionals for surface science: exchange-correlation model development with Bayesian error estimation. Phys. Rev. B 85, 235149 (2012).
Acknowledgements
Support from the US Department of Energy Office of Basic Energy Science to the SUNCAT Center for Interface Science and Catalysis is gratefully acknowledged. The research of A.A.L. was conducted with Government support under and awarded by DoD, Air Force Office of Scientific Research, National Defense Science and Engineering Graduate (NDSEG) Fellowship, 32 CFR 168a. A.R.K. acknowledges the computing resources from the Carbon High-Performance Computing Cluster at Argonne National Laboratory under proposal CNM-46405. C.T. acknowledges support from the National Science Foundation Graduate Research Fellowship Program (GRFP) Grant DGE-114747. J.H.M. acknowledges funding from the NSF GRFP, grant number DGE-114747, and also the Center of Nanostructuring for Efficient Energy Conversion (CNEEC) at Stanford University, an Energy Frontier Research Center funded by the US Department of Energy, Office of Basic Energy Sciences under award number DE-SC0001060. J.S.Y. appreciates the financial support from the US DOS via the International Fulbright Science & Technology Award programme. H.A. receives funding from Aramco Services Company.
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A.A.L., A.R.K., H.A., J.S.Y. and J.H.M. performed the DFT calculations; A.A.L. and A.R.K. analysed the results and prepared the manuscript. All authors contributed to the discussion and approved the manuscript. A.A.L. and A.R.K. contributed equally to this work.
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Latimer, A., Kulkarni, A., Aljama, H. et al. Understanding trends in C–H bond activation in heterogeneous catalysis. Nature Mater 16, 225–229 (2017). https://doi.org/10.1038/nmat4760
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DOI: https://doi.org/10.1038/nmat4760
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