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Title: Impact of nonadiabatic charge transfer on the rate of redox chemistry of carbon oxides on rutile TiO2 (110) surface

We present the results of a density functional theory (DFT) within the LDA+U approximation on large models of partially reduced TiO2 (110) rutile surface to investigate the nature of charge transfer and the role of non-adiabatic effects on three prototypical redox reactions: (i) O2 adsorption (ii) CO oxidation and (iii) CO2 reduction. Charge-constrained DFT (cDFT) is used to estimate kinetic parameters for a Marcus theory rate law that accounts for adiabatic coupling effects on reaction rates. We find that for O2 adsorption, the coupling between adiabatic states is strong, leading to fast charge transfer rates. The lowest energy structures at high coverage consist of two chemisorbed O2-, one adsorbed at a VO site and the other adsorbed at an adjacent Ti5C site. For CO oxidation, however, all reactions are kinetically hindered on the ground state due to the weak adiabatic coupling at the state crossing, such that one has to overcome two kinetically unfavorable charge transfer events to drive the process (non-adiabatically) on the thermal ground state. The process can be driven by photochemical means but would result in an adsorbed radical [OCOO-] intermediate species. Similarly, CO2 reduction also proceeds via a non-adiabatic charge transfer to form an adsorbed CO2-more » species followed by a second non-adiabatic charge transfer to produce CO. Our analysis provides important computational guidelines for modeling these types of processes. We thank Z. Dohnalek, M. Hendersen, G. Kimmel, H. Metieu, and N. Petrik for invaluable discussions. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle. Computational resources were provided at W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL and the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory.« less
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Journal Article
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Journal Name: ACS Catalysis, 5(3):1764-1771
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Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
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Country of Publication:
United States
charge transfer; non-adiabatic effects; rutile TiO2; Marcus theory