RESUMO
Atomically dispersed precious metals on oxide supports have recently become increasingly interesting catalytic materials. Nonetheless, their non-trivial preparation and limited thermal and environmental stability constitutes an issue for their potential applications. Here we demonstrate that an oxygen plasma pre-treatment of the ceria (CeO2 ) surface serves to anchor Pt single atoms, making them active and resistant towards sintering in the CO oxidation reaction. Through a combination of experimental results obtained on well-defined CeO2 films and theory, we show that the O2 plasma causes surface nanostructuring and the formation of surface peroxo (O2 2- ) species, favoring the uniform and dense distribution of isolated strongly bonded Pt2+ atoms. The promotional effect of the plasma treatment was further demonstrated on powder Pt/CeO2 catalysts. We believe that plasma functionalization can be applied to other metal/oxide systems to achieve tunable and stable catalysts with a high density of active sites.
RESUMO
Electron transfer with changing occupation in the 4f subshell poses a considerable challenge for quantitative predictions in quantum chemistry. Using the example of cerium oxide, we identify the main deficiencies of common parameter-dependent one-electron approaches, such as density functional theory (DFT) with a Hubbard correction, or hybrid functionals. As a response, we present the first benchmark of ab initio many-electron theory for electron transfer energies and lattice parameters under periodic boundary conditions. We show that the direct random phase approximation clearly outperforms all DFT variations. From this foundation, we, then, systematically improve even further. Periodic second-order Møller-Plesset perturbation theory meanwhile manages to recover standard hybrid functional values. Using these approaches to eliminate parameter bias allows for highly accurate benchmarks of strongly correlated materials, the reliable assessment of various density functionals, and functional fitting via machine-learning.
RESUMO
The physical and chemical properties of oxides are defined by the presence of oxygen vacancies. Experimentally, non-defective structures are almost impossible to achieve due to synthetic constraints. Therefore, it is crucial to account for vacancies when evaluating the characteristics of these materials. The electronic structure of oxygen-depleted oxides deeply differs from that of the native forms, in particular, of reducible metal oxides, where excess electrons can localize in various distinct positions. In this perspective, we present recent developments from our group describing the complexity of these defective materials that highlight the need for an accurate description of (i) intrinsic vacancies in polar terminations, (ii) multiple geometries and complex electronic structures with several states attainable at typical working conditions, and (iii) the associated dynamics for both vacancy diffusion and the coexistence of more than one electronic structure. All these aspects widen our current understanding of defects in oxides and need to be adequately introduced in emerging high-throughput screening methodologies.
RESUMO
The catalytic activity of metals supported on oxides depends on their charge and oxidation state. Yet, the determination of the degree of charge transfer at the interface remains elusive. Here, by combining density functional theory and first-principles molecular dynamics on Pt single atoms deposited on the CeO2 (100) surface, we show that the common representation of a static metal charge is oversimplified. Instead, we identify several well-defined charge states that are dynamically interconnected and thus coexist. The origin of this new class of strong metal-support interactions is the relative position of the Ce(4f) levels with respect to those of the noble metal, allowing electron injection to (or recovery from) the support. This process is phonon-assisted, as the Ce(4f) levels adjust by surface atom displacement, and appears for other metals (Ni) and supports (TiO2). Our dynamic model explains the unique reactivity found for activated single Pt atoms on ceria able to perform CO oxidation, meeting the Department of Energy 150 °C challenge for emissions.
