Competitive C–C and C–H bond scission in the ethanol oxidation reaction on Cu(100) and the effect of an alkaline environment
文献信息
Chuan-Jian Zhong
Direct ethanol fuel cell technology is impeded by inefficient, yet expensive anode catalysts. As such, research on effective and cheap anode catalysts towards complete ethanol oxidation reaction (EOR) is greatly needed. Herein, we report the investigations of the competitive C–C and C–H bond scissions in the EOR involving CH3CO, CH2CO, and CHCO species on Cu(100) using density functional theory and transition state theory calculations. The easiest C–C bond cleavage was found in CH2CO while the most difficult C–H bond cleavage was also found in CH2CO, both with an activation energy of 1.02 eV. The feasible C–C bond scission may take place in CH2CO with a rate constant ratio of the C–C to the C–H bond scission at 100 °C of 0.32. Furthermore, in an alkaline environment, the C–H bond scission activation barrier is considerably lowered but the C–C bond cleavage activation barrier is slightly increased for both CH3CO and CH2CO species. The reaction of CH3CO species on Cu(100) under alkaline conditions produces mainly acetic acid with a barrier of 0.49 eV and a rate constant of 4.93 × 105 s−1 at 100 °C.
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来源期刊
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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