.png){kind=icon}
.png){kind=icon}
Return
Quantifying the Impact of Metal Population Distribution in MFI-Supported Mo Catalysts for Methane Dehydroaromatization
.png){kind=icon}
OA
AI
E
A
K
S
S
DOI：10.1021/acscatal.6c02024.png)
.png){kind=icon}
Original request for help.png){kind=icon}
Share.png){kind=icon}
Save
Abstract
En 中文
Precise evaluation of intrinsic kinetic behavior in Mo/MFI catalysts for methane dehydroaromatization (MDA) is confounded by variations in Mo dispersion and speciation, which are influenced by metal loading and zeolite acidity. This work advances the utility of H2-temperature programmed reduction (H2-TPR) for characterizing Mo/MFI catalysts by enabling quantitative comparison of MoOx populations distinguished by reduction behavior and linked to initial catalytic performance. A comprehensive H2 reduction pathway is established through systematic H2-TPR studies varying catalyst composition (1–10 wt % Mo, Si/Al = 15, 40, ∞), supplemented by UV-Raman spectroscopy, X-ray powder diffraction, N2 physisorption, NH3-TPD, and advanced spectroscopic analysis (in situ XAS with principal component analysis/multivariate curve resolution—alternating least squares). Two low-temperature H2-TPR regions capture distinct Mo populations undergoing initial Mo(VI) → Mo(IV) reduction: a lower-temperature population (Mo-RI) associated primarily with highly dispersed, anchored MoOx species expected to predominantly reside within MFI channels, and a higher-temperature population (Mo-RII) corresponding to a broader set of MoOx species that becomes increasingly bulk-like/extrazeolitic at higher Mo loading. Quantification of these populations provides practical, kinetically relevant descriptors for comparing initial MDA rates across catalysts with varying Mo loading, Si/Al ratio, and MoOx heterogeneity. Application of lower-temperature Mo-RI estimates to kinetic measurements reveals a minimum threshold of ∼0.12 × 10–3 mol Mo-RI/gcat, above which initial forward benzene rates normalized to this population converge despite differences in metal loading and zeolite Brønsted acidity. This threshold coincides with a transition toward a common C2-mediated benzene-forming regime, as indicated by approach-to-equilibrium analysis of methane-to-ethane, ethane-to-ethylene, and ethylene-to-benzene reaction steps. Above this threshold, normalized initial benzene rates are nearly invariant with increasing Mo-RII/Mo-RI population ratio, indicating that excess Mo-RII populations, including bulk-like/extrazeolitic MoOx domains present at higher loading, do not measurably suppress benzene formation associated with anchored and mostly channel-confined Mo population under the initial-rate conditions examined.
Keywords:
methane dehydroaromatization
Mo/MFI
zeolite catalysis
molybdenum speciation
temperature-programmed reduction
in situ XAS
Journal
IF:
13.1
Papers:
1.6W
Citations:
15.0W
Organization
Cited Papers