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Theoretical investigation of the mechanism of ethanol to propene catalyzed by phosphorus-modified FAU zeolite

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Abstract

The reaction mechanism of ethanol to propene (ETP) on phosphorus-modified acidic FAU (H-FAU) zeolite has been theoretically investigated by a two-layer ONIOM (our Own N-layered Integrated molecular Orbital and molecular Mechanics) method. The ETP mechanism is divided into four reaction pathways from I to IV. The calculated data suggest that the rate-determining steps are the dehydration of ethanol (for pathways I and II) and the ethylation of propene (for pathways III and IV). Different reaction steps are in the following order of reactivity: dimerization > proton transfer ≥ deprotonation > beta-scission > ethylation > dehydration of ethanol. Pathways I and II have almost the same reactivity as pathways III and IV. The addition of phosphorus atom decreases the energy barriers of elementary steps and is more favorable for the ETP process than the acidic Si/Al zeolite without phosphorus modification. The differential charge density (DCD), local orbital locator (LOL) and reduced density gradient (RDG) plots reveal the electron migration and the nature of transition states. The RDG plots show that there are attractive and spatial repulsive van der Waals (VDW) interactions between different organic fragments of TSs. The DCD analysis reveals that the electrons migrate from an organic fragment to another fragment. The LOL maps suggest that there are weak covalent interactions between the atoms in the forming or breaking chemical bonds.

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Funding

This work was financially supported by Development Foundation for young and middle-aged scientific talents of Shanghai Institute of Technology (Project Number ZQ2022-4), the National Natural Science Foundation of China (Project Number 21203118, 22008155, 22075183, 21878188 and 21975161), IIASA Young Scientists Summer Program (Project Number 21411140044), Science and Technology Commission of Shanghai Municipality Project (Project Number 18090503800), Shuguang Program of Shanghai Education Development Foundation and Shanghai Municipal Education Commission (Project Number 18SG52), Chenguang Program of Shanghai Education Development Foundation and Shanghai Municipal Education Commission (Project Number 19CG69), the Talent Development Foundation of Shanghai (Project Number 2018034), Shanghai Gaofeng & Gaoyuan Project for University Academic Program Development, the Research Fund of Department of Education of Sichuan Province (No. 18ZB0481), Development of integrated membrane technology for deep treatment of ammonia nitrogen wastewater from rare earth industry (J2018-61), Development of Metal-supported Catalysts for Thiophene Desulfurization (J2019-360), Simulation of Thermal Conductivity of Polymer Matrix Composites (J2020-50–2), Natural Science Foundation of Shanghai (No.19ZR1454900).

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Authors and Affiliations

  1. School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai, 201418, China

    Qiaoxian Tong, Mengya Xia, Yingxin Sun & Sheng Han

  2. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 201418, China

    Huai Sun

  3. College of Chemistry and Material Science, Sichuan Normal University, Chengdu, 610068, China

    Qianggen Li

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Qiaoxian Tong wrote the main manuscript text and prepared all figures and tables. Yingxin Sun, Sheng Han, and Qianggen Li contributed to conceptualization. All authors reviewed the manuscript.

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214_2022_2911_MOESM1_ESM.pdf

Free energy profiles of pathways II, III, and IV, optimized structures of all the TSs and intermediates, plots of DCDs, RDGs, and LOLs (Figures S1 to S51) (Supplementary file1 (PDF 4673 KB)).

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Tong, Q., Xia, M., Sun, H. et al. Theoretical investigation of the mechanism of ethanol to propene catalyzed by phosphorus-modified FAU zeolite. Theor Chem Acc 141, 54 (2022). https://doi.org/10.1007/s00214-022-02911-8

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