Metal-ceria interactions and catalytic activity: A theoretical perspective

SENANAYAKE, SANJAYA D.; P. G. LUSTEMBERG; M. V. GANDUGLIA-PIROVANO; RODRIGUEZ, JOSÉ A.

Santa FE

Conferencia; VI San Luis Conference on Surfaces, Interfaces and Catalysis; 2018

Ceria (CeO2) is the most significant of the oxides of rare-earth elements in industrial catalysis with its reducibility being essential to its functionality in catalytic applications. The complexity of real (powder) catalysts hinders the fundamental understanding of how they work. For instance, in the case of metal nanoparticles on ceria supports, it is known that metal-oxide interactions can dramatically influence catalytic activity. To unravel the effect of the support, well-defined ceria-based model catalysts are prepared experimentally or created theoretically and studied. The basic questions that need to be answered are then, how does the presence of a ceria support modifies catalytic activity?, what is the effect of metal loading?, and what is the role of both metal and oxide in the reaction mechanism? In this work, recent results on ceria-supported Ni, Co and Cu model catalysts will be discussed, 1-3 as examples of catalysts for methane dry reforming (DRM: CH4+CO22H2+2CO). Also, the Ni/ceria system is considered for the effect of water on C-H bond breaking in the selectivity from methane to methanol formation (CH4+1/2O2CH3OH).4 The emphasis is here put on theoretical studies and special attention is given to the effects of ceria as catalyst support.AcknowledgementWe thank Zongyuan Liu, Ramón A. Gutiérrez, John J. Carey, Michael Nolan, Robert M. Palomino, Mykhailo Vorohta, David C. Grinter, Pedro J. Ramírez, Vladimir Matolín, H. Fabio Busnengo, Javier Carrasco, Jing Zhou, Dario J. Stacchiola, Ethan J. Crumlin, Si Luo, Iradwikanari Waluyo, Thuy-Duong Nguyen-Phan, David López-Durán, Tomá? Duchoň, and Jaime Evans for their contributions to this work.References1. Liu, Z.; Grinter, D. C.; Lustemberg, P. G.; Nguyen-Phan, T.-D.; Zhou, Y.; Luo, S.; Waluyo, I.; Crumlin, E. J.; Stacchiola, D. J.; Zhou, J.; Carrasco, J.; Busnengo, H. F.; Ganduglia-Pirovano, M. V.; Senanayake, S. D.; Rodriguez, ? Dry Reforming of Methane on a Highly-Active Ni-CeO2 Catalyst: Effects of Metal-Support Interactions on C−H Bond Breaking? J. A. Angew. Chem., Int. Ed., 55, 7455−7459, 2016.2. Lustemberg, P. G.; Ramírez, P. J.; Liu, Z.; Gutiérrez, R. A.; Grinter, D. G.; Carrasco, J.; Senanayake, S. D.; Rodriguez, J. A.; Ganduglia-Pirovano, M. V., "Room-Temperature Activation of Methane and Dry Re-forming with CO2 on Ni-CeO2(111) Surfaces: Effect of Ce3+ Sites and Metal?Support Interactions on C?H Bond Cleavage", ACS Catal., 6, 8184 ? 8191, 2016.3. Liu, Z.; Lustemberg, P. G.¸ Gutiérrez, R. A.¸ Carey, J. J.; Palomino, R. M.; Vorokhta, M.; Grinter, D. C.; Ramírez, P. J.; Matolín, V.; Nolan, M.; Ganduglia-Pirovano, M. V.; Senanayake, S. D.; Rodriguez, J. A." In Situ Investigation of Methane Dry Reforming on Metal/Ceria(111) Surfaces: Metal?Support Interactions and C−H Bond Activation at Low Temperature" Angew. Chem. Int. Ed., 56, 13041? 13046, 2017.4. Lustemberg, P. G.; Palomino; R. M., Gutiérrez, R. A.; Grinter, D. C.; Vorokhta, M.; Liu, Z.; Ramírez, P. J.; Matolín, V.; Ganduglia-Pirovano, M. V.; Senanayake, S. D.; Rodriguez, J. A., ?Catalytic Conversion of Methane to Methanol on Ni-Ceria Surfaces: Effect of Water on C-H Bond Breaking and Selectivity towards Methanol Formation?, in preparation.