Molecular Design of Supported MoOx Catalysts with Surface TaOx Promotion for Olefin Metathesis

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

doi:10.1021/acscatal.1c06000

Title: Molecular Design of Supported MoO_x Catalysts with Surface TaO_x Promotion for Olefin Metathesis

Journal Article · 22 February 2022 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.1c06000 · OSTI ID:1866116

^[1]; Xiang, Shuting ^[2];

^[2];

^[1]

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

A series of supported 3% MoOx catalysts were synthesized by incipient-wetness impregnation of 5%-15% TaO_x surface modified γ-Al₂O₃ support. The catalysts were characterized by in situ spectroscopies (DRIFTS, Raman, UV-vis, XAS) and multiple chemical probes (C₂H₄/C₄H₈ titration, C₃H₆-TPSR, steady state propylene metathesis, NH₃-IR adsorption). The supported tantalum oxide phase was present as surface TaO_x sites on the γ-Al₂O₃ support that capped that Al₂O₃ surface hydroxyls. The change in available surface hydroxyls caused the subsequent anchoring of MoOx species to occur at different surface hydroxyls. This shifted the anchoring of MoO_x species from basic (Al-OH) to neutral (Al₂-OH) to more acidic (Al₃-OH) surface hydroxyls as well as perturbation of the remaining alumina surface hydroxyls by the surface TaO_x sites. The TaO_x surface modified γ-Al₂O₃ support increased the number of activated surface MoO_x sites (Ns) by ~6x and the TOF by ~10x resulting in an increased activity of ~60x. In conclusion, It was found that the specific anchoring surface hydroxyls rather than the extent of oligomerization of the surface MoO_x sites control the number of activated MoO_x sites and TOF for propylene metathesis. No relationship between the nature of the surface Lewis/Brønsted acid sites and Ns and TOF were found to be present.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; FG02-93ER14350

OSTI ID:: 1866116

Report Number(s):: BNL-222959-2022-JAAM

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 5 Vol. 12; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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