Nature of Hydride Species at the Surface of Ga-Based Oxides Used in the Methanol-Mediated Syngas to Light Olefins Conversion
Abstract
Ga-based oxide catalysts have recently been proposed as an alternative to Zn-based oxides for the methanol-mediated syngas to light olefins conversion through the OXZEO process, due to their high capacity to produce CH3OH intermediate and concomitant weaker activity for olefins hydrogenation. In this work, the nature and reactivity of surface Ga-H species were investigated by comparing in situ/operando DRIFTS measurements and DFT calculations to assess their role in achieving such selective hydrogenation. Like -Ga2O3, GaZr mixed oxides were shown to favor formation of isolated gallium hydrides tri-coordinated to oxygen anions (Gatri-H) via a heterolytic dissociation mechanism of H2, with moderate but sufficient capacity to hydrogenate HCOO* to CH3OH. In contrast, on -Ga2O3, both homolytic and heterolytic dissociative pathways of H2 led to Gatri-H species in close proximity which were found much less stable and hence, more prone to unselective hydrogenation reactions. These metastable gallium hydrides on coordinatively unsaturated Ga cations are proposed to strongly reduce the olefins selectivity in the OXZEO process but should be efficient for other reactions requiring consecutive (des)hydrogenation steps.
Related
- Role of coupling and zeolite acidity in the methanol-mediated CO2 conversion to olefins over ZnZrOx-AEI zeolite tandem catalysis
- Valorization of Coal Fly Ash into Fe-FAU Catalysts: Targeted Iron Recovery and Fly Ash Matrix Effects in Methane-to-Methanol Conversion
- Electroanalytical and Computational Investigation of Oxoammonium-Mediated Hydride Transfer.
- Resolving Active Sites in Cu/ZnO Methanol Synthesis via Coupled Modelling of Surface Reconstruction and Coverage-dependent Kinetics
- Ultramild conversion of nitrobenzene to aniline mediated by metal organic alloy NiGraf in green solvent
BibTeX
@article{salichon2026nature,
title = {{Nature of Hydride Species at the Surface of Ga-Based Oxides Used in the Methanol-Mediated Syngas to Light Olefins Conversion}},
author = {A. Salichon and D. Loffreda and P. Afanasiev and S. Loridant},
journal = {ACS Catalysis},
year = {2026},
month = sep,
doi = {10.1021/acscatal.6c02789},
url = {https://hal.science/hal-05763826v1},
note = {CC BY-NC-SA 4.0},
}
RIS
TY - JOUR
TI - Nature of Hydride Species at the Surface of Ga-Based Oxides Used in the Methanol-Mediated Syngas to Light Olefins Conversion
AU - A. Salichon
AU - D. Loffreda
AU - P. Afanasiev
AU - S. Loridant
PY - 2026
DA - 2026/09/25
JO - ACS Catalysis
DO - 10.1021/acscatal.6c02789
UR - https://hal.science/hal-05763826v1
AB - Ga-based oxide catalysts have recently been proposed as an alternative to Zn-based oxides for the methanol-mediated syngas to light olefins conversion through the OXZEO process, due to their high capacity to produce CH3OH intermediate and concomitant weaker activity for olefins hydrogenation. In this work, the nature and reactivity of surface Ga-H species were investigated by comparing in situ/operando DRIFTS measurements and DFT calculations to assess their role in achieving such selective hydrogenation. Like -Ga2O3, GaZr mixed oxides were shown to favor formation of isolated gallium hydrides tri-coordinated to oxygen anions (Gatri-H) via a heterolytic dissociation mechanism of H2, with moderate but sufficient capacity to hydrogenate HCOO* to CH3OH. In contrast, on -Ga2O3, both homolytic and heterolytic dissociative pathways of H2 led to Gatri-H species in close proximity which were found much less stable and hence, more prone to unselective hydrogenation reactions. These metastable gallium hydrides on coordinatively unsaturated Ga cations are proposed to strongly reduce the olefins selectivity in the OXZEO process but should be efficient for other reactions requiring consecutive (des)hydrogenation steps.
SN - 2155-5435
SN - 2155-5435
ER -