催化作用
醋酸
化学
羧酸
掺杂剂
无机化学
碳氢化合物
密度泛函理论
有机化学
兴奋剂
计算化学
材料科学
光电子学
作者
Mingxia Zhou,Aimee L. Church,Michael J. Cordon,Chenyang Li,Rodney D. Hunt,Jae‐Soon Choi,Lei Bai,Zhenglong Li,James E. Parks,Michael Z. Hu,Larry A. Curtiss,Rajeev S. Assary
出处
期刊:ACS Sustainable Chemistry & Engineering
[American Chemical Society]
日期:2022-08-16
卷期号:10 (34): 11068-11077
被引量:3
标识
DOI:10.1021/acssuschemeng.1c06675
摘要
Carboxylic acid ketonization has recently gained significant attention to produce biomass-derived hydrocarbon fuels as it not only removes the highly reactive carboxylic functional group but also increases the size of the carbon chain. In this study, Ca-doped CeO2-based catalysts were investigated for acetic acid ketonization using a combined experimental and computational approach. Acetic acid conversion was performed across a range of temperatures including higher temperatures relevant to catalytic hot gas filtration (450 °C). Ca addition slightly decreases overall acetic acid ketonization reactivity yet stabilizes the catalyst at the higher temperatures necessary for catalytic hot gas filtration. From density functional theory calculations of the ketonization reaction mechanism, the C–C coupling and water formation steps are identified as two of the most energy-consuming steps on a CeO2 surface with a proximal oxygen vacancy and the presence of a Ca dopant stabilizes the key intermediates. Calculations predict an optimal structure comprising three Ca ensembles to minimize the reaction free energies for C–C coupling and water formation steps. These findings provide a priori information to guide future experiments for ketonization catalyst design and development.
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