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The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO₂ Catalysts.

ABSTRACT: Electronic metal-support interactions (EMSI) describe the electron flow between metal sites and a metal oxide support. It is generally used to follow the mechanism of redox reactions. In this study of CuO-CeO₂ redox, an additional flow of electrons from metallic Cu to surface carbon species is observed via a combination of operando X-ray absorption spectroscopy, synchrotron X-ray powder diffraction, near ambient pressure near edge X-ray absorption fine structure spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. An electronic metal-support-carbon interaction (EMSCI) is proposed to explain the reaction pathway of CO oxidation. The EMSCI provides a complete picture of the mass and electron flow, which will help predict and improve the catalytic performance in the selective activation of CO₂ , carbonate, or carbonyl species in C1 chemistry.

SUBMITTER: Kang L

PROVIDER: S-EPMC8251948 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The thermal deactivation of Pd/CeO2-ZrO2 (Pd/CZ) three-way catalysts was studied via nanoscale structural characterization and catalytic kinetic analysis to obtain a fundamental modeling concept for predicting the real catalyst lifetime. The catalysts were engine-aged at 600-1100 °C and used for chassis dynamometer driving test cycles. Observations using an electron microscope and chemisorption experiments showed that the Pd particle size significantly changed in the range of 10-550 nm as a function of aging temperatures. The deactivated catalyst structure was modeled using different-sized hemispherical Pd particles that were in intimate contact with the support surface. Therefore, Pd/CZ contained two types of surface Pd sites residing on the surface of a hemisphere (Pds) and circular periphery of the Pd/CZ interface (Pdb), whereas a reference catalyst, Pd/Al2O3, contained only Pds. In all Pd particle sizes investigated herein, Pd/CZ exhibited higher reaction rates than Pd/Al2O3, which nonlinearly increased with increasing slope as the weight-based number of surface-exposed Pd atoms ([Pds] + [Pdb]) increased. This finding contrasted with that of Pd/Al2O3, where the reaction rate linearly increased with [Pds]. When the Pds sites in both catalysts were equivalent in terms of their specific activities, the activity difference between Pd/CZ and Pd/Al2O3 corresponded to the contribution from Pdb, where oxygen storage/release to/from CZ played a key role. This contribution linearly increased with [Pdb] and therefore decreased with Pd sintering. Although both Pds and Pdb sites showed nearly constant turnover frequencies despite the difference in the Pd particle size, the values for Pdb were more than 2 orders of magnitude greater than those for Pds when assuming a single-atom width one-dimensional Pdb row model. These results suggest that the thermal deterioration of the three-phase boundary site, where Pd, CZ, and the gas phase meet, determines the activity under surface-controlled conditions.

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The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO₂ Catalysts.

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The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO2 Catalysts.

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OmicsDI is part of the ELIXIR infrastructure

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The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO₂ Catalysts.