A mechanistic study of the electrochemical oxygen reduction on the model semiconductor n-Ge(100) by ATR-IR and DFT
文献情報
Simantini Nayak, P. Ulrich Biedermann, Martin Stratmann, Andreas Erbe
The electrochemical oxygen reduction reaction (ORR) on a n-Ge(100) surface in 0.1 M HClO4 was investigated in situ and operando using a combination of attenuated total reflection infrared (ATR-IR) spectroscopy and density functional (DFT) calculations. The vibrational modes of the detected intermediates were assigned based on DFT calculations of solvated model clusters such as Ge-bound superoxides and peroxides. ATR-IR shows the Ge-bound superoxide with a transition dipole moment oriented at (28 ± 10)° with respect to the surface normal. At slightly negative potentials, the surface-bound peroxide is identified by an OOH bending mode as a further intermediate, oriented at a similar angle. At strongly negative potentials, a surface-bound perchlorate is found. The findings indicate a multistep mechanism of the ORR. The reaction is furthermore coupled with the hydrogen evolution reaction (HER).
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Physical Chemistry Chemical Physics

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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