Rare-earth stabilized oxygen-vacancy-rich TiO2 urchin-like hollow spheres for synergistic photoelectrocatalytic methanol oxidation

Rare-earth-stabilized oxygen vacancies unlock highly active Pt/TiO 2 photoelectrocatalysts. • Urchin-like hollow TiO 2 spheres maximize defect exposure, light harvesting, and mass transport. • All rare-earth-doped catalysts outperform undoped OV-THS/Pt in methanol oxidation. • OV-Pr-THS/Pt achieves 5793 and 8790 mA mg −1 under dark and light, respectively. • Pr doping and oxygen-vacancy engineering synergistically accelerate charge transfer and MOR kinetics. Pt-based catalysts with high activity and durability are essential for direct methanol fuel cells. While TiO 2 substrates offer promise for photoelectrocatalytic methanol oxidation, their performance is limited by poor charge separation and slow kinetics. In this work, oxygen-vacancy-rich rare-earth-doped TiO 2 urchin-like hollow spheres (Nd, Eu, Ce, and Pr) were constructed as advanced supports for Pt nanoparticles, enabling simultaneous regulation of defect chemistry and morphology. Among the prepared catalysts, OV-Pr-THS/Pt exhibits the best activity, delivering 5793 mA mg −1 in the dark and 8790 mA mg −1 under light irradiation, markedly higher than the undoped counterpart. These findings demonstrate that the synergistic integration of rare-earth doping and oxygen-vacancy engineering provides an effective strategy for designing high-performance photoelectrocatalysts for sustainable energy conversion. Download: Download high-res image (126KB) Download: Download full-size image