Tuning the Number of Active Sites and Turnover Frequencies by Surface Modification of Supported ReO4/(SiO2–Al2O3) Catalysts for Olefin Metathesis

Zhang, Bin; Lwin, Soe; Xiang, Shuting; Frenkel, Anatoly I.; Wachs, Israel E.

doi:10.1021/acscatal.0c05279

Title: Tuning the Number of Active Sites and Turnover Frequencies by Surface Modification of Supported ReO₄/(SiO₂–Al₂O₃) Catalysts for Olefin Metathesis

Journal Article · Mon Feb 08 00:00:00 EST 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c05279· OSTI ID:1775287

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Lehigh Univ., Bethlehem, PA (United States)
Stony Brook Univ., NY (United States)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

A series of supported ReO_x catalysts were synthesized by incipient-wetness impregnation of perrhenic acid onto one component (Al₂O₃ and SiO₂) and surface modified mixed oxide supports (SiO₂/Al₂O₃, Al₂O₃/SiO₂, and ZSM-5 (Si/Al=15)), characterized with in situ molecular spectroscopy (Raman, DRIFTS, UV-vis and XAS) and chemically probed (ammonia chemisorption, C₂H₄/C₄H₈-titration, C₃H₆-TPSR and steady-state propylene self-metathesis). The initial dehydrated surface rhenia species were coordinated to the oxide supports as isolated Re⁷⁺O₄ sites. For the Al-containing supports, dioxo surface (O=)₂Re(-O)₂ sites appear to be the preferred coordination. The number of activated surface ReO_x sites during metathesis is determined by the oxide support ligands (3%ReO_x/ZSM-5 > 3%ReO_x/5%AlO_x/SiO₂ > 3%ReO_x/5%SiO_x/Al₂O₃ > 3%ReO_x/Al₂O₃ ~ 3%ReO_x/SiO₂). The specific activity (TOF) is also controlled by the oxide support ligands (3%ReO_x/Al₂O₃ > 3%ReO_x/5%SiO_x/Al₂O₃ >> 3%ReO_x/ZSM-5 ~ 3%ReO_x/5%AlO_x/SiO₂ >> 3%ReO_x/SiO₂). The overall propylene metathesis activity (N × TOF), however is dominated by the number of activated sites (Ns). Consequently, the enhanced overall activity of surface ReO_x supported on SiO₂-Al₂O₃ mixed oxide supports is related to the greater number of activated surface ReO_x sites. Furthermore, the overall propylene metathesis activity was not related to the local surface ReO₄ molecular structure or strength of the Brønsted acid site since the same rhenia structures appeared to be present on all of the active catalysts and the strength of the Brønsted acid sites were comparable for all of the active catalysts, respectively.

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Research Organization:: Lehigh Univ., Bethlehem, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-93ER14350; SC0012335

OSTI ID:: 1775287

Journal Information:: ACS Catalysis, Vol. 11, Issue 4; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Tuning the Number of Active Sites and Turnover Frequencies by Surface Modification of Supported ReO4/(SiO2–Al2O3) Catalysts for Olefin Metathesis

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Title: Tuning the Number of Active Sites and Turnover Frequencies by Surface Modification of Supported ReO₄/(SiO₂–Al₂O₃) Catalysts for Olefin Metathesis