Effects of CO2 adsorption on proton migration on a hydrated ZrO2 surface: an ab initio molecular dynamics study

Literature Information

Publication Date 2017-07-03
DOI 10.1039/C7CP01650F
Impact Factor 3.676
Authors

Ryuhei Sato, Yasushi Shibuta, Fuyuki Shimojo, Shu Yamaguchi


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Abstract

Hydration reactions on a carbonate-terminated cubic ZrO2(110) surface were analyzed using ab initio molecular dynamics (AIMD) simulations. After hydration reactions, carbonates were still present on the surface at 500 K. However, these carbonates are very weak conjugate bases and only act as steric hindrance in proton hopping processes between acidic chemisorbed H2O molecules (Zr–OH2) and monodentate hydroxyl groups (Zr–OH−). Similar to a carbonate-free hydrated surface, Zr–OH2, Zr–OH−, and polydentate hydroxyl groups (OH+) were observed, while the ratio of acidic Zr–OH2 was significantly larger than that on the carbonate-free hydrated surface. A thermodynamic discussion and bond property analysis reveal that CO2 adsorption significantly decreases the basicity of surface oxide ions (O), whereas the acidity of Zr–OH2 is not affected. As a result, protons released from OH+ react with Zr–OH− to form Zr–OH2, leading to a deficiency of proton acceptor sites, which decreases the proton conductivity by the hopping mechanism.

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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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