Atomic and electronic structure of molybdenum carbide phases: bulk and low Miller-index surfaces

文献情報

出版日 2013-05-29

DOI 10.1039/C3CP51389K

インパクトファクター 3.676

著者

Francesc Viñes, Jose A. Rodriguez, Francesc Illas

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要旨

The geometric and electronic structure of catalytically relevant molybdenum carbide phases (cubic δ-MoC, hexagonal α-MoC, and orthorhombic β-Mo2C) and their low Miller-index surfaces have been investigated by means of periodic density functional theory (DFT) based calculations with the Perdew–Burke–Ernzerhof (PBE) exchange–correlation functional. Comparison to available experimental data indicates that this functional is particularly well suited to study these materials. The calculations reveal that β-Mo2C has a stronger metallic character than the other two polymorphs, both β-Mo2C and δ-MoC have a large ionic contribution, and δ- and α-MoC exhibit the strongest covalent character. Among the various surfaces explored, the calculations reveal the high stability of the δ-MoC(001) nonpolar surface, Mo- and C-terminated (001) polar surfaces of α-MoC, and the nonpolar (011) surface of β-Mo2C. A substantially low work function of only 3.4 eV is predicted for β-Mo2C(011), suggesting that this system is particularly well suited for (electro)catalytic processes where surface → adsorbate electron transfer is essential. The overall implications for heterogeneously catalysed reactions by these molybdenum carbide nanoparticles are also discussed.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.