Nanostructured TiO 2 is one of the best materials for photocatalysis, thanks to its high surface area and surface reactivity, but its large energy bandgap (3.2 eV) hinders the use of the entire solar spectrum. Here, it is proposed that defect-engineered nanostructured TiO 2 photocatalysts are obtained by hydrogenation strategy to extend its light absorption up to the near-infrared region. It is demonstrated that hydrogenated or colored TiO 2 hollow spheres (THS) composed of hierarchically assembled nanoparticles result in much broader exploitation of the solar spectrum (up to 1200 nm) and the engineered surface enhances the photogeneration of charges for photocatalytic processes. In turn, when applied for photodegradation of a targeted drug (Ciprofloxacin) this results in 82% degradation after 6 h under simulated sunlight. Valence band analysis by photoelectron spectroscopy revealed the presence of oxygen vacancies, whose surface density increases with the hydrogenation rate. Thus, a tight correlation between degree of hydrogenation and photocatalytic activity is directly established. Further insight comes from electron paramagnetic resonance, which evidences bulk Ti 3+ centers only in hydrogenated THS. The results are anticipated to disclose a new path toward highly efficient photocatalytic titania in a series of applications targeting water remediation and solar fuel production.
Basic insight into the structural evolution of electrocatalysts under operating conditions is of substantial importance for designing water oxidation catalysts. The first‐row transition metal‐based catalysts present state‐of‐the‐art oxygen evolution reaction (OER) performance under alkaline conditions. Apparently, confinement has become an exciting strategy to boost the performance of these catalysts. The van der Waals (vdW) gaps of transition metal dichalcogenides are acknowledged to serve as a suitable platform to confine the first‐row transition metal catalysts. This study focuses on confining Ni(OH)2 nanoparticle in the vdW gaps of 2D exfoliated SnS2 (Ex‐SnS2) to accelerate water oxidation and to guarantee long term durability in alkaline solutions. The trends in oxidation states of Ni are probed during OER catalysis. The in situ studies confirm that the confined system produces a favorable environment for accelerated oxygen gas evolution, whereas the un‐confined system proceeds with a relatively slower kinetics. The outstanding OER activity and excellent stability, with an overpotential of 300 mV at 100 mA cm−2 and Tafel slope as low as 93 mV dec−1 results from the confinement effect. This study sheds light on the OER mechanism of confined catalysis and opens up a way to develop efficient and low‐cost electrocatalysts.
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