Probing hydrodesulfurization over bimetallic phosphides using monodisperse Ni2-xMxP nanoparticles encapsulated in mesoporous silica

Metal phosphide nanoparticles encapsulated in mesoporous silica provide a well-defined system for probing the fundamental chemistry of the hydrodesulfurization (HDS) reaction over this new class of hydrotreating catalysts. To investigate composition effects in bimetallic phosphides, the HDS of dibenzothiophene (DBT) was carried out over a series of Ni-rich Ni2-xMxP@mSiO(2) (M = Co, Fe) nanocatalysts (x <= 0.50). The Ni2-xMxP nanoparticles (average diameters: 11-13 nm) were prepared by solution-phase arrested precipitation and encapsulated in mesoporous silica, characterized by a range of techniques (XRD, TEM, IR spectroscopy, BET surface area, CO chemisorption) and tested for DBT HDS activity and selectivity. The highest activity was observed for a Ni1.92Co0.08P@mSiO(2) nanocatalyst, but the overall trend was a decrease in HDS activity with increasing Co or Fe content. In contrast, the highest turnover frequency (TOF) was observed for the most Co- and Fe-rich compositions based on sites titrated by CO chemisorption. IR spectral studies of adsorbed CO on the Ni2-xMxP@mSiO(2) catalysts indicate that an increase in electron density occurs on Ni sites as the Co or Fe content is increased, which may be responsible for the increased TOFs of the catalytic sites. The Ni2-xMxP@mSiO(2) nanocatalysts exhibit a strong preference for the direct desulfurization pathway (DDS) for DBT HDS that changes only slightly with increasing Co or Fe content. (C) 2015 Elsevier B.V. All rights reserved.