Influence of Ti‐incorporated Zeolite Topology and Pore Condensation on Vapor Phase Propylene Epoxidation Kinetics with Gaseous H 2 O 2

Kwon, Ohsung; Zeynep Ayla, E.; Potts, David S.; Flaherty, David W.

doi:10.1002/ange.202405950

Title: Influence of Ti‐incorporated Zeolite Topology and Pore Condensation on Vapor Phase Propylene Epoxidation Kinetics with Gaseous H ₂ O ₂

Journal Article · 17 June 2024 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202405950 · OSTI ID:2373256

^[1]; Zeynep Ayla, E. ^[1];

^[1];

^[2]

Department of Chemical and Biomolecular Engineering University of Illinois Urbana-Champaign Urbana IL 61801 USA
Department of Chemical and Biomolecular Engineering University of Illinois Urbana-Champaign Urbana IL 61801 USA, School of Chemical and Biomolecular Engineering Georgia Institute of Technology Atlanta GA 30332 USA

Abstract Vapor‐phase propylene (C ₃ H ₆ ) epoxidation kinetics with hydrogen peroxide (H ₂ O ₂ ) strongly reflects the physical properties of Ti‐incorporated zeolite catalysts and the presence of spectating molecules (“solvent”) near active sites even without a bulk liquid phase. Steady‐state turnover rates of C ₃ H ₆ epoxidation and product selectivities vary by orders of magnitudes, depending on the zeolite silanol ((SiOH) _x ) density, pore topology (MFI, *BEA, FAU), and the quantity of condensed acetonitrile (CH ₃ CN) molecules nearby active sites, under identical reaction mechanisms sharing activated H ₂ O ₂ intermediates on Ti surfaces. Individual kinetic analyses for propylene oxide (PO) ring‐opening, homogeneous diol oxidative cleavage, and homogeneous aldehyde oxidation reveal that secondary reaction kinetics following C ₃ H ₆ epoxidation responds more sensitively to the changes in zeolite physical properties and pore condensation with CH ₃ CN. Thus, higher PO selectivities achieved in hydrophilic Ti‐MFI at steady‐state reflect the preferential stabilization of transition states for C ₃ H ₆ epoxidation (a primary reaction) relative to PO ring‐opening and oxidative cleavage (secondary reactions) that solvation effects that reflect interactions among condensed CH ₃ CN within pores and the extended pore structure.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; SC0020224

OSTI ID:: 2373256

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 30 Vol. 136; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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