Zr-modified SBA-15 as an electronic support to modulate activity and selectivity of NiW catalysts in dibenzothiophene hydrodesulfurization

In this study, Zr-modified SBA-15 materials were synthesized and used as support for NiW catalysts in the hydrodesulfurization (HDS) of dibenzothiophene (DBT). Systematic variation of Zr content (3–20 wt%) allowed for correlation of structural, electronic, and acidic properties with catalytic performance. Incorporation of Zr increased Lewi acidity and altered the electronic environment of the NiW active phase (UV-Vis, Py-FTIR), improving metal dispersion and HDS activity; the catalyst with five wt% Zr displayed the highest initial reaction rate (2.83 × 10− 7 molDBT·gcat-1·s-1). Although direct desulfurization (DDS) remains the prevailing pathway (HYD/DDS < 1 for all samples), moderate Zr addition significantly increases the hydrogenation contribution (the HYD fraction raises from 0.17 to 0.28), indicating that Zr tunes the HYD/DDS balance via electronic and acidic modulation of the support. These results reveal a practical strategy for tuning the activity and selectivity of NiW catalysts by engineering metal-support interactions. The graphical abstract is a schematic representation intended to illustrate qualitative trends rather than an exact atomic-scale structure. Zr-modified SBA-15 materials were synthesized and employed as supports for NiW catalysts in dibenzothiophene hydrodesulfurization. Zirconium incorporation increased Lewis acidity and altered the electronic properties of the SBA-15 support. An optimal Zr loading (5 wt%) yielded the highest initial HDS reaction rate (2.83 × 10⁻⁷ molDBT·gcat⁻¹·s⁻¹). Moderate Zr contents enhanced the hydrogenation contribution while maintaining direct desulfurization as the dominant pathway (HYD/DDS < 1). The results demonstrate that controlled Zr modification enables tuning of catalytic activity and selectivity through support-mediated metal–support interactions.