Elucidating the role of $\mathrm{Fe}$-$\mathrm{Mo}$ interactions in the metal oxide precursors for Fe promoted $\mathrm{Mo/ZSM}$-5 catalysts in non-oxidative methane dehydroaromatization

Hossain, Md Sifat; Dhillon, Gagandeep Singh; Liu, Liping; Sridhar, Apoorva; Hiennadi, Emanuele J.; Hong, Jiyun; Bare, Simon R.; Xin, Hongliang; Ericson, Thomas; Cozzolino, Anthony; Khatib, Sheima J.

doi:10.1016/j.cej.2023.146096

Elucidating the role of $$\mathrm{Fe}$$-$$\mathrm{Mo}$$ interactions in the metal oxide precursors for Fe promoted $$\mathrm{Mo/ZSM}$$-5 catalysts in non-oxidative methane dehydroaromatization

Journal Article · Wed Sep 20 00:00:00 EDT 2023 · Chemical Engineering Journal

DOI:https://doi.org/10.1016/j.cej.2023.146096· OSTI ID:2311851

Hossain, Md Sifat ^[1]; Dhillon, Gagandeep Singh ^[2]; ^[3]; Sridhar, Apoorva ^[4]; ^[3]; ^[5]; Bare, Simon R. ^[5]; Xin, Hongliang ^[3]; Ericson, Thomas ^[6]; ^[6]; ^[3]

Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States); SLAC
Texas Tech University, Lubbock, TX (United States); Lydian Labs Inc., Cambridge, MA (United States)
Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States)
Texas Tech University, Lubbock, TX (United States); Intel Co, Hillsboro, OR (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Texas Tech University, Lubbock, TX (United States)

Literature shows that adding Fe as a separate phase to MoO₃/ZSM-5 catalysts can improve benzene selectivity in methane dehydroaromatization (MDA), but only when added in small quantities, making it difficult to characterize the state of Fe in the catalyst and understand the role of Fe-Mo interactions on the catalytic properties. We explore how the nature of the Mo-Fe interactions in the catalyst precursor can influence the stability and product selectivity in MDA, by employing for the first time Fe₂(MoO₄)₃/ZSM-5 as a catalyst precursor in MDA. We have compared the activity of Fe₂(MoO₄)₃/ZSM-5 with monometallic MoO₃/ZSM-5 and mixed MoO₃ + Fe₂O₃/ZSM-5 containing equivalent Mo and Fe loadings and found that Fe₂(MoO₄)₃/ZSM-5 shows higher benzene selectivity than the mixed MoO₃ + Fe₂O₃/ZSM-5 catalyst and exhibits higher stability in reaction compared to the monometallic MoO3/ZSM-5 catalyst. Structural characterization suggests that Fe₂(MoO₄)₃ partially segregates to Fe₂O₃and amorphous MoO_x during thermal pretreatment. The MoO_x species migrate into the zeolite channels during pretreatment, while Fe oxides remain on the external surface of the zeolite. Gas adsorption/desorption techniques and density functional theory calculations demonstrate that the preexisting Fe₂O₃ phases on the external surface of the zeolite in the mixed MoO₃ + Fe₂O₃/ZSM-5 precursor trap (MoO₃)₃ clusters preventing them from migrating into the zeolite channels during pretreatment, whereas gradual formation of amorphous MoOx together with the segregation of the Fe₂O₃ phase when using the Fe₂(MoO₄)₃ precursor diminishes trapping of (MoO₃)₃ and consequently enhances migration and anchoring of the MoO_x species in the zeolite channels, boosting selectivity to benzene. Characterization of used catalysts suggests that the presence of Fe promotes formation of structured carbon nanofibers which reduce the rate of catalyst deactivation.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

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

Grant/Contract Number:: AC02-76SF00515; EE0009412; SC0019074; SC0023323

OSTI ID:: 2311851

Alternate ID(s):: OSTI ID: 2318711
OSTI ID: 2007084

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Vol. 475; ISSN 1385-8947

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Elucidating the role of $$\mathrm{Fe}$$-$$\mathrm{Mo}$$ interactions in the metal oxide precursors for Fe promoted $$\mathrm{Mo/ZSM}$$-5 catalysts in non-oxidative methane dehydroaromatization

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