Gas-phase surface modification to control catalyst structure and yields in methane dehydroaromatization

Ramos-Yataco, Jordy; Zhang, Xinrui; Alayoglu, Selim; Pham, Hien N.; Datye, Abhaya K.; Marks, Tobin J.; Notestein, Justin

doi:10.1016/j.micromeso.2024.113227

Gas-phase surface modification to control catalyst structure and yields in methane dehydroaromatization

Journal Article · Thu Jun 20 00:00:00 EDT 2024 · Microporous and Mesoporous Materials

DOI:https://doi.org/10.1016/j.micromeso.2024.113227· OSTI ID:2482303

Ramos-Yataco, Jordy ^[1]; Zhang, Xinrui ^[1]; Alayoglu, Selim ^[1]; Pham, Hien N. ^[2]; ^[2]; Marks, Tobin J. ^[1]; ^[3]

Northwestern University, Evanston, IL (United States)
University of New Mexico, Albuquerque, NM (United States)
Northwestern University, Evanston, IL (United States); University of New Mexico, Albuquerque, NM (United States)

Methane dehydroaromatization (MDA) is a promising approach for direct methane transformation to aromatics and hydrogen. The benchmark catalyst Mo/H-ZSM-5 struggles to find commercial adoption because of thermodynamically-limited yields and rapid coking on Brønsted acid and molybdenum carbide species, especially on zeolite external surfaces. Here, gas-phase atomic layer deposition (ALD) overcoats H-ZSM-5 external surfaces with SiO₂ or Al₂O₃. NH₃-TPD, HRTEM, and textural properties show that these overcoats exclusively passivate zeolite external surfaces. Under MDA conditions, SiO₂ gives softer coke and increases cumulative benzene yields by 25%, while Al₂O₃ strongly decreases yields. H₂-TPR and UV-visible and Raman spectroscopy show how the overcoats redisperse the MoO_x precatalysts, especially over multiple deactivation and isothermal oxidative regeneration cycles. Combined with ²⁷Al-MAS NMR, MoO_x redistribution and dealumination are seen as the causes of long-term deactivation over multiple regeneration cycles, and this process continues to occur regardless of the overcoat. Altogether, the deposition of a small amount of silica on the outer surface of Mo/H-ZSM-5 reduces the formation of hard coke, which could be regenerated by milder methods such as hydrogen treatment.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern University, Evanston, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: FG02-03ER15457

OSTI ID:: 2482303

Alternate ID(s):: OSTI ID: 2377786

Journal Information:: Microporous and Mesoporous Materials, Journal Name: Microporous and Mesoporous Materials Vol. 377; ISSN 1387-1811

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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