Vacancy-mediated diffusion of carbon in cobalt and its influence on COactivation
文献信息
Qiuju Zhang, Liang Chen, Ping Cui, Xiaoqing Pan
We present a theoretical understanding of carbon deposition and diffusion in FCC and HCP cobalt from first principles. We found that the deposited carbon atom can readily penetrate into the first sub-layer of Co substrates, while further diffusion into deeper interstices seems unfeasible. In the presence of cobalt vacancy, the carbon diffusion can be greatly promoted and possibly leads to the carburization of cobalt catalysts. The infiltrated carbon atoms have a pronounced influence on the catalytic activity toward CO adsorption and dissociation. Compared to the clean cobalt surfaces, the C–O bond is less weakened on the carburized cobalt due to the depletion of Co-d electrons. As a result, the activation barrier for CO dissociation is substantially increased. We suggest that the carburization is another important cause to the deactivation of Co-based catalysts in addition to the site blockage by the surface carbon deposition.
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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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