Catalytic enhancement in dissociation of nitric oxide over rhodium and nickel small-size clusters: a DFT study

Literature Information

Publication Date 2014-01-22
DOI 10.1039/C3CP54667E
Impact Factor 3.676
Authors

Chun-Chih Chang, Jia-Jen Ho


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Abstract

We applied density-functional theory (DFT) to investigate the adsorption and dissociation of NO on Rh19 and Ni19 clusters with a double-icosahedral (DI) structure. The transition structures of the NO dissociating on the potential-energy surfaces were derived using the nudged-elastic-band (NEB) method. The adsorption energies of NO molecules on the rhombus-center region of DI clusters are −2.53 eV and −2.78 eV with the N–O bond elongated to 1.33 Å and 1.35 Å, respectively, on Ni19 and Rh19, compared to 1.16 Å of the gaseous NO counterpart. The barriers to dissociation of N–O on both DI-Rh19 (Ea = 0.24 eV) and DI-Ni19 (Ea = 0.42 eV) clusters are small, indicating that the rhombus-center region of DI metal clusters might activate the scission of the N–O bond. To understand the interaction between these nanocluster catalysts and their adsorbates, we calculated the electronic properties including the local densities of states, orbital evolution of the adsorbates and interaction energies; the results indicate that a profound catalytic behavior for bond scission is observed in this unique rhombus-center region of DI metal-nanoclusters.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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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.

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