Ethylene Dehydroaromatization over Ga-ZSM-5 Catalysts: Nature and Role of Gallium Speciation

Zhou, Yunwen; Thirumalai, Hari; Smith, Scott K.; Whitmire, Kenton H.; Liu, Jing; Frenkel, Anatoly I.; Grabow, Lars C.; Rimer, Jeffrey D.

doi:10.1002/anie.202007147

Ethylene Dehydroaromatization over Ga-ZSM-5 Catalysts: Nature and Role of Gallium Speciation

Journal Article · Mon Aug 03 00:00:00 EDT 2020 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202007147· OSTI ID:1657464

Zhou, Yunwen ^[1]; ^[2]; Smith, Scott K. ^[2]; ^[3]; ^[4]; ^[5]; ^[2]; ^[2]

Univ. of Houston, TX (United States); Stony Brook University
Univ. of Houston, TX (United States)
Rice Univ., Houston, TX (United States)
Manhattan College, Riverdale, NY (United States)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Bifunctional catalysis in zeolites possessing both Brønsted and Lewis acid sites offers unique opportunities to tailor shape selectivity and enhance catalyst performance. In this work, we examine the impact of framework and extra-framework gallium species on enriched aromatics production in zeolite ZSM-5. In this study we compare three distinct methods of preparing Ga-ZSM-5 and reveal direct (single step) synthesis leads to optimal catalysts compared to post-synthesis methods. Using a combination of state-of-the-art characterization, catalyst testing, and density functional theory calculations, we show that Ga Lewis acid sites strongly favor aromatization. Our findings also suggest Ga(framework) – Ga(extra-framework) pairings, which can only be achieved in materials prepared by direct synthesis, are the most energetically favorable sites for reaction pathways leading to aromatics. Calculated acid site exchange energies between extra-framework Ga at framework sites comprised of either Al or Ga reveal a site-specific preference for stabilizing Lewis acids, which is qualitatively consistent with experimental measurements. These findings indicate the possibility of tailoring Lewis acid siting by the placement of Ga heteroatoms at distinct tetrahedral sites in the zeolite framework, which can have a marked impact on catalyst performance relative to conventional H-ZSM-5.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Stony Brook Univ., NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS); Welch Foundation

Grant/Contract Number:: AC02-05CH11231; SC0001004; SC0011983; SC0012704

OSTI ID:: 1657464

Alternate ID(s):: OSTI ID: 1760480
OSTI ID: 1661577
OSTI ID: 1786175
OSTI ID: 1670662

Report Number(s):: BNL-219898-2020--JAAM

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 44 Vol. 59; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Ethylene Dehydroaromatization over Ga‐ZSM‐5 Catalysts: Nature and Role of Gallium Speciation

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Lewis acid
acid siting
aromatics
bifunctional catalysis
zeolite synthesis

Ethylene Dehydroaromatization over Ga-ZSM-5 Catalysts: Nature and Role of Gallium Speciation

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