Surface‐Dependent Activation of Model α‐Al2O3‐Supported P‐Doped Hydrotreating Catalysts Prepared by Spin Coating - Archive ouverte HAL
Article Dans Une Revue Chemistry - A European Journal Année : 2020

Surface‐Dependent Activation of Model α‐Al2O3‐Supported P‐Doped Hydrotreating Catalysts Prepared by Spin Coating

Résumé

Requirements for improved catalytic formulations is continuously driving research in hydrotreating (HDT) catalysis for biomass upgrading and heteroatom removal for cleaner fuels. The present work proposes a surface-science approach for the understanding of the genesis of the active (sulfide) phase in model P-doped MoS2 hydrotreating catalysts supported on α-Al2O3 single crystals. This approach allows one to obtain a surface-dependent insight by varying the crystal orientations of the support. Model phosphorus-doped catalysts are prepared via spin-coating of Mo–P precursor solutions onto four α-Al2O3 crystal orientations, C(0001), A(1120), M(1010) and R(1102) that exhibit different speciations of surface -OH. 31P and 95Mo liquid-state NMR are used to give a comprehensive description of the Mo and P speciation of the phospho-molybdic precursor solution. The speciation of the deposition solution is then correlated with the genesis of the active MoS2 phase. XPS quantification of the surface P/Mo ratio reveal a surface-dependent phosphate aggregation driven by the amount of free phosphates in solution. Phosphates aggregation decreases in the following order C(0001)≫M(1010) > A(1120), R(1102). This evolution can be rationalized by an increasing strength of phosphate/surface interactions on the different α-Al2O3 surface orientations from the C(0001) to the R(1102) plane. Retardation of the sulfidation with temperature is observed for model catalysts with the highest phosphate dispersion on the surface (A(11200), R(1102)), suggesting that phosphorus strongly intervene in the genesis of the active phase through a close intimacy between phosphates and molybdates. The surface P/Mo ratio appears as a key descriptor to quantify this retarding effect. It is proposed that retardation of sulfidation is driven by two effects: i) a chemical inhibition through formation of hardly reducible mixed molybdo-phosphate structures and ii) a physical inhibition with phosphate clusters inhibiting the growth of MoS2. The surface-dependent phosphorus doping on model α-Al2O3 supports can be used as a guide for the rational design of more efficient HDT catalysts on industrial γ-Al2O3 carrier.
Fichier principal
Vignette du fichier
Surface-dependent activation.pdf (1.9 Mo) Télécharger le fichier
Surface-Dependent Activation Supp Material.pdf (2.11 Mo) Télécharger le fichier
Origine Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-04025167 , version 1 (05-04-2023)

Identifiants

Citer

Ricardo Garcia de Castro, Jérémy Bertrand, Baptiste Rigaud, Elodie Devers, Mathieu Digne, et al.. Surface‐Dependent Activation of Model α‐Al2O3‐Supported P‐Doped Hydrotreating Catalysts Prepared by Spin Coating. Chemistry - A European Journal, 2020, 26 (64), pp.14623-14638. ⟨10.1002/chem.202001882⟩. ⟨hal-04025167⟩
94 Consultations
19 Téléchargements

Altmetric

Partager

More