Excess charge driven dissociative hydrogen adsorption on Ti2O4−

Literature Information

Publication Date 2017-08-02
DOI 10.1039/C7CP03798H
Impact Factor 3.676
Authors

Min Gao, Satoshi Maeda, Sandy Gewinner, Wieland Schöllkopf, Knut R. Asmis, Andrey Lyalin


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Abstract

The mechanism of dissociative D2 adsorption on Ti2O4−, which serves as a model for an oxygen vacancy on a titania surface, is studied using infrared photodissociation spectroscopy in combination with density functional theory calculations and a recently developed single-component artificial force induced reaction method. Ti2O4− readily reacts with D2 under multiple collision conditions in a gas-filled ion trap held at 16 K forming a global minimum-energy structure (DO–Ti–(O)2–Ti(D)–O)−. The highly exergonic reaction proceeds quasi barrier-free via several intermediate species, involving heterolytic D2-bond cleavage followed by D-atom migration. We show that, compared to neutral Ti2O4, the excess negative charge in Ti2O4− is responsible for the substantial lowering of the D2 dissociation barrier, but does not affect the molecular D2 adsorption energy in the initial physisorption step.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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