文献类型：期刊文献

英文题名：Optimization of activity and selectivity for syngas-to-ethanol conversion on metal-based catalysts via the first-principles microkinetic simulations

作者：Li, Aoran[1,2];Lai, Zhuangzhuang[1,2];Hu, Peijun[1,2];Wang, Haifeng[1,2]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China

年份：2024

卷号：564

外文期刊名：MOLECULAR CATALYSIS

收录：;EI(收录号：20242516289961);WOS:【SCI-EXPANDED(收录号:WOS:001298893200001)】；

基金：Acknowledgements This project was supported by National Key R&D & D Program of China (2021YFA1500700) , NSFC (22203031, 91945302, and 92045303) , and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Density functional theory calculation; Ethanol synthesis; Syngas conversion; Microkinetic analysis; Catalyst design

摘要：Achieving high selectivity in converting syngas to ethanol has long been a challenging task, requiring identification of key factors favoring ethanol production over other by-products such as methane, methanol, and acetaldehyde. Herein, we perform systematic density functional theory (DFT) calculations and microkinetic simulations to shed light on the activity and selectivity trends of ethanol relative to three competing by-products in syngas conversion, which quantitatively unveils the key determining factors on the transition metal-based catalysts. The scaling relations involved are revealed as functions of the adsorption energies of C and O species (EC E C and E O ), and the three-dimensional activity and selectivity surfaces are constructed quantitatively, indicating that the optimal condition (peak position) correspond to E C =-6.10 eV and E O =-5.70 eV. Furthermore, we find that ethanol activity at the peak is primarily constrained by the kinetic barriers of CH3O 3 O dissociation and the coupling reaction of CH3 3 and CO, while its selectivity can be enhanced by increasing the energy barrier of CH3 3 hydrogenation and strengthening the adsorption of CH3CHO. 3 CHO. More significantly, following these rules, the single-atom metal alloy catalysts (i.e., Cu1Co, 1 Co, Cu1Ni) 1 Ni) are identified that could serve as promising candidates for ethanol synthesis, which are superior to the common alloy-type catalysts. We believe that these insights further deepen the understanding of theoretical design of metal alloy catalysts in ethanol production.