Unveiling the Function of Oxygen Vacancy on Facet-Dependent CeO for the Catalytic Destruction of Monochloromethane: Guidance for Industrial Catalyst Design.

Environ Sci Technol

Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental and Resource Sciences, Zhejiang University, 866 Yuhangtang Road, Hangzhou 310058, P. R. China.

Published: May 2024

AI Article Synopsis

  • Secondary pollution from chlorinated volatile organic compounds (CVOCs) poses significant challenges, and experimental and theoretical approaches were used to study how different shapes of ceria (CeO) impact the destruction of monochloromethane (MCM).
  • Results showed that ceria nanorods with the (110) facet are the most effective at destroying MCM, with vacancies aiding in the activation of MCM molecules.
  • Analysis indicated that the key reactions involve electron transfer and that the hydrogen chloride produced mainly comes from the methyl group in MCM, with water's role being to help in the desorption of the generated hydrogen chloride.

Article Abstract

Secondary pollution remains a critical challenge for the catalytic destruction of chlorinated volatile organic compounds (CVOCs). By employing experimental studies and theoretical calculations, we provide valuable insights into the catalytic behaviors exhibited by ceria rods, cubes, and octahedra for monochloromethane (MCM) destruction, shedding light on the elementary reactions over facet-dependent CeO. Our findings demonstrate that CeO nanorods with the (110) facet exhibit the best performance in MCM destruction, and the role of vacancies is mainly to form a longer distance (4.63 Å) of frustrated Lewis pairs (FLPs) compared to the stoichiometric surface, thereby enhancing the activation of MCM molecules. Subsequent molecular orbital analysis showed that the adsorption of MCM mainly transferred electrons from the 3 and 4* orbitals to the Ce 4f orbitals, and the activation was mainly caused by weakening of the 3 bonding orbitals. Furthermore, isotopic experiments and theoretical calculations demonstrated that the hydrogen chloride generated is mainly derived from methyl in MCM rather than from water, and the primary function of water is to form excess saturated H on the surface, facilitating the desorption of generated hydrogen chloride.

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http://dx.doi.org/10.1021/acs.est.4c00297DOI Listing

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