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通过将铈引入莫来石氧化物YMnO中促进丙烷的低温氧化

Promotion of Low-Temperature Oxidation of Propane through Introduction of Ce into Mullite Oxide YMn O.

作者信息

Zhang Tong, Dong Anqi, Wan Xiang, Shi Guoliang, Peng Jianfei, Li Weifang, Wang Gen, Chen Da, Wang Weichao

机构信息

College of Electronic and Information Engineering, Shandong University of Science and Technology, Qingdao, 266590, P. R. China.

Integrated Circuits and Smart System Lab (Shenzhen), Renewable Energy Conversion and Storage Center, Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology, College of Electronic Information and Optical Engineering, Nankai University, Tianjin, 300071, P. R. China.

出版信息

Chempluschem. 2022 Feb;87(2):e202100455. doi: 10.1002/cplu.202100455.

Abstract

A high-surface-area Ce doped mullite YMn O was developed via a facile hydrothermal approach, which exhibited higher catalytic activity with a long thermal stability towards propane oxidation in regards to pristine mullite YMn O . T (the temperature at 90 % conversion of reactant) of propane over the mixed oxides is ∼40 °C lower than that over pristine YMn O mullite (147 m /g). The complete oxidation temperature occurs at as low as 225 °C (1000 ppm C H and 10 % O balanced with N , WHSV=30,000 mL/g h). Notably, the mixed oxides maintain superior catalytic stability at 250 °C for 120 h without noticeable loss in the activity. Fundamentally, the remarkable performance stems from the abundant oxygen defects caused by the lattice mismatch between CeO and YMn O , which is conducive to the gas phase oxygen adsorption and activation, thereby enhancing the low temperature catalytic activity of the material. In addition, the CeO on the catalyst's surface acts as an oxygen reservoir and provides additional adsorption sites for propane to promote the oxidation reaction. In situ DRIFTS results indicates that the dissociation of acrylate could be the key step for propane oxidation since acrylate is more difficult to decompose and desorb than formate and acetate. These findings revealed the roles of ceria on mullite oxides for propane oxidation activity.

摘要

通过简便的水热法制备了高比表面积的铈掺杂莫来石YMnO,与原始莫来石YMnO相比,该材料对丙烷氧化表现出更高的催化活性和较长的热稳定性。混合氧化物上丙烷的T(反应物转化率为90%时的温度)比原始YMnO莫来石(147 m²/g)低约40°C。完全氧化温度低至225°C(1000 ppm C₃H₈和10% O₂与N₂平衡,WHSV = 30,000 mL/g·h)。值得注意的是,混合氧化物在250°C下保持优异的催化稳定性达120小时,活性无明显损失。从根本上讲,卓越的性能源于CeO₂与YMnO之间晶格失配导致的大量氧缺陷,这有利于气相氧的吸附和活化,从而提高了材料的低温催化活性。此外,催化剂表面的CeO₂充当氧库,并为丙烷提供额外的吸附位点以促进氧化反应。原位DRIFTS结果表明,丙烯酸盐的解离可能是丙烷氧化的关键步骤,因为丙烯酸盐比甲酸盐和乙酸盐更难分解和解吸。这些发现揭示了二氧化铈在莫来石氧化物上对丙烷氧化活性的作用。

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