Interface-engineered ZrO2@W2C-WOx heterojunctions with a built-in electric field for selective, 1O2-dominated oxidative desulfurization

The non-selective decomposition of hydrogen peroxide into hydroxyl radicals often plagues heterogeneous oxidation, critically limiting its chemoselectivity for applications like oxidative desulfurization (ODS). Here, we demonstrate a strategy to program the H 2 O 2 activation pathway by designing a ZrO 2 @W 2 C-WO x heterostructure. Interfacial electron transfer from ZrO 2 to W 2 C establishes a built-in electric field, inducing an amorphous, mixed-valent WO x shell. This unique electronic interface enables synergistic dual-site activation of H 2 O 2 at adjacent Zr and WO x motifs, promoting a surface peroxo-intermediate pathway that selectively yields singlet oxygen ( 1 O 2 ). The catalyst exhibits a high turnover frequency (TOF) of 470 h −1 for ODS under mild conditions. Crucially, it demonstrates exceptional chemoselectivity, with reactive oxygen species (ROS) partitioning dominated by 1 O 2 ( 1 O 2  ≫ •O 2 −  > •OH). This selectivity ensures robust performance across high sulfur loadings (500–2000 ppm S) and in the presence of fuel-relevant interferents. The catalyst's proven stability and low leaching highlight its industrial potential. By engineering an interfacial charge-transfer heterojunction with a built-in electric field coupled with a redox-active WO x shell, this work provides a blueprint for steering ROS generation toward non-radical pathways for precise, selective oxidation.