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CeO/CoO 界面上的表面吸附和晶格氧促进增强的催化炭烟燃烧:实验和理论研究。

Surface adsorbed and lattice oxygen activated by the CeO/CoO interface for enhancive catalytic soot combustion: Experimental and theoretical investigations.

机构信息

College of Light Chemical Industry and Materials Engineering, Shunde Polytechnic, Foshan 528333, China.

College of Light Chemical Industry and Materials Engineering, Shunde Polytechnic, Foshan 528333, China.

出版信息

J Colloid Interface Sci. 2023 May 15;638:109-122. doi: 10.1016/j.jcis.2023.01.124. Epub 2023 Jan 28.

Abstract

Metal oxide-oxide interface on supported catalyst has been rarely studied due to the complex interfacial structure and synthetic challenge. Herein, different Ag-supported CeO/CoO samples with various covered-state of CeO were prepared for catalytic soot oxidation. In comparison, catalytic activity was significantly improved by grafting CeO on CoO, in which the best performing Ag/CoCe-2 exhibited remarkable catalytic performance towards soot oxidation with a T of 290.5 ℃ under 10 % O/N. Catalyst characterization investigated by Scanning Electron Microscope (SEM), quasi in-situ X-ray Photoelectron Spectroscopy (XPS), in-situ Raman, etc. revealed that this outstanding promotion in catalytic activity can be principally ascribed to the formation of the CeO/CoO interface. An appropriate CeO dosage maximized the contact and interaction between CoO and CeO, resulting in the largest CeO/CoO interface featured with abundant generated superoxide species and activated surface lattice oxygen. Density functional theory (DFT) calculations were also carried out for the oxygen vacancy formation energy, Gibbs free energy, etc. In presence of the CeO/CoO interface, a charge density redistribution around the adsorbed reactants at oxygen vacancies could be formed, owing to the efficient charge transfer enhanced by the electron-appealing effect. The change in electronic structure favored reducing the oxygen vacancy formation energy and boosting the lattice oxygen activation induced by the hybridized Co-O-Ce bonds, finally lowering the adsorption and activation barriers for reactive species and accelerating the reaction kinetics.

摘要

由于复杂的界面结构和合成挑战,负载型催化剂中金属氧化物-氧化物界面很少被研究。本文制备了不同的负载型 Ag-CeO/CoO 催化剂,研究了 CeO 的不同覆盖状态对催化炭烟氧化的影响。与 CoO 相比,CeO 接枝到 CoO 上显著提高了催化活性,其中表现最好的 Ag/CoCe-2 在 10% O/N 条件下,T 为 290.5℃时具有显著的炭烟氧化催化性能。通过扫描电子显微镜(SEM)、准原位 X 射线光电子能谱(XPS)、原位拉曼等手段对催化剂进行了表征,结果表明,这种优异的催化活性提升主要归因于 CeO/CoO 界面的形成。适量的 CeO 可以最大化 CoO 和 CeO 之间的接触和相互作用,从而形成最大 CeO/CoO 界面,具有丰富的超氧物种和活化的表面晶格氧。还进行了密度泛函理论(DFT)计算,研究了氧空位形成能、吉布斯自由能等。在 CeO/CoO 界面的存在下,由于电子吸引效应增强的有效电荷转移,在吸附反应物周围的氧空位处可以形成电荷密度重新分布。电子结构的变化有利于降低氧空位形成能,促进杂化 Co-O-Ce 键引起的晶格氧活化,最终降低反应物种的吸附和活化能垒,加速反应动力学。

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