Engineering High‐Density Ti Single‐Atom Sites via Steric‐Electrostatic Repulsion on Hierarchical Hollow Silica Spheres for Near‐Atom‐Efficiency Oxidative Desulfurization

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ABSTRACT Oxidative desulfurization (ODS) offers a promising route to ultra‐clean fuels but is limited by low atomic utilization, mass‐transfer constraints, and instability of active sites at high loadings. Here, we report a scalable steric–electrostatic repulsion strategy for constructing high‐density, non‐zeolitic Ti single‐atom catalysts with fully accessible active sites. By co‐engineering a peroxo‐titanium precursor with strong electrostatic repulsion and hierarchical hollow silica spheres with maximized external surface area, Ti‐O‐Ti condensation is suppressed while diffusion limitations are eliminated. This enables the stabilization of atomically dispersed TiO 4 /TiO 6 sites exclusively on accessible surfaces. The resulting catalyst achieves near‐atom‐efficiency ODS, delivering complete conversion of 500 ppm dibenzothiophene within 5 min, a turnover frequency of 148.28 h −1 , and a low apparent activation energy of 23.78 kJ·mol −1 , along with excellent stability and regenerability. Spectroscopic analyses confirm the atomic dispersion and coordination environments, while density functional theory (DFT) calculations reveal distinct reaction pathways and identify a Ti‐η 2 ‐OO‐tBu intermediate governing rapid oxidation. This work establishes a generalizable precursor‐support co‐engineering paradigm for high‐loading single‐atom catalysts and provides fundamental and practical insights relevant to energy‐efficient catalysis and sustainable chemical manufacturing.

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Related topics: Catalysis and Hydrodesulfurization Studies · Catalytic Processes in Materials Science · Catalysis and Oxidation Reactions