Dissociative iodomethane adsorption on Ag-MOR and the formation of AgI clusters: an ab initio molecular dynamics study

Literature Information

Publication Date 2017-09-18
DOI 10.1039/C7CP05562E
Impact Factor 3.676
Authors

Jean-François Paul, Laurent Cantrel, Michael Badawi


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Abstract

Radioactive iodine species belong to the most dangerous components of nuclear effluents and waste produced by nuclear facilities. In this work, we use computer simulations at the periodic DFT level to investigate dissociative adsorption of iodomethane on silver-exchanged mordenite, which is among the most effective sorbents of iodine species available today. The structure, energetics, and mobility of complexes Ag–(CH3I) and Ag–(CH3I)2 formed upon adsorption of iodomethane on Ag+ sites are investigated using the ab initio MD approach. The free-energy profiles for the reaction CH3I + Ag-MOR → AgI + CH3-MOR are determined using the blue moon ensemble technique. The AgI species formed as a product of dissociative adsorption are shown to combine spontaneously into small clusters (AgI)n with the dimensions restricted by the size and geometry of confining voids. The structure and energetics of the (AgI)n species are analysed in detail and compared with the available experimental and theoretical data. The internal energy of formation of clusters in mordenite is shown to contribute significantly to the shift of equilibrium from the undissociated to dissociated form of adsorbed CH3I.

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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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