Computational Design of Metal-Exchanged MFI Zeolites for Coupling CO2–Ethylene to Form Acrylic Acid

Masood, Zaheer; Nguyen, Quy P.; Wang, Bin

doi:10.1021/acssuschemeng.3c08535

Title: Computational Design of Metal-Exchanged MFI Zeolites for Coupling CO₂–Ethylene to Form Acrylic Acid

Journal Article · 21 March 2024 · ACS Sustainable Chemistry & Engineering

DOI: https://doi.org/10.1021/acssuschemeng.3c08535 · OSTI ID:2326350

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Univ. of Oklahoma, Norman, OK (United States); University of Oklahoma
Univ. of Oklahoma, Norman, OK (United States)

The production of acrylic acid by coupling CO₂ and ethylene is highly desirable, as it uses a C₁ molecule to introduce the carboxylic group into a large commodity chemical, forming an unsaturated carboxylic acid. Molecular complexes have been used as catalysts in the literature for this reaction; however, these homogeneous studies were all limited by low activity and stability, and efficient heterogeneous catalysts remain to be explored. Here, we report density functional theory calculations, through which we investigated metal-exchanged MFI zeolites with metals from 3d, 4d, and 5d series for this reaction. Screening of reaction thermodynamics has shown that Sc, Y, Cr, Mo, W, Mn, Tc, and Re dispersed into MFI zeolites are potential catalysts. We further calculated the activation barriers for the β–H transfer, a key elementary step that normally determines the overall rates, and found the lowest barrier over Sc- and Y-MFI; such a feasible kinetics is attributed to the low electronegativity of Sc and Y that strongly affects the nature of the transition states and the charge redistribution during the β–H transfer. In conclusion, this work thus provides guidelines for designing a zeolite-based catalyst for this valuable reaction and identifies promising metal centers to be used.

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Research Organization:: Univ. of Oklahoma, Norman, OK (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0023448

OSTI ID:: 2326350

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 18 Vol. 12; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
carboxylation
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zeolites
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hydrogen transfer

Title: Computational Design of Metal-Exchanged MFI Zeolites for Coupling CO2–Ethylene to Form Acrylic Acid

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Title: Computational Design of Metal-Exchanged MFI Zeolites for Coupling CO₂–Ethylene to Form Acrylic Acid