Tuning the reactivity of TiO_(2)layer with uniform distribution of Sub-5 nm Fe_(2)O_(3)particles via in situ voltage-assisted oxidation for robust catalytic reduction

The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.

Nucleation and growth behavior of coating film on Mg–Al–Zn alloy with different surface topographies via plasma electrolytic oxidation

This work was made to investigate how nucleation and growth behavior of the coating film were affected by surface topographies of Mg–Al–Zn alloy substrate during the initial stage of plasma electrolytic oxidation(PEO).To satisfy this end,a single substrate was prepared by mechanical treatment exhibiting rough and smooth regions with an equal area on the surface.The rough region with prominent hills and grooves induced the breakdown of passive film,which was indicated by an early appearance of plasma discharge on the rough region since nucleation of coating film occurred preferentially around the hills.However,the coating film grown on the grooves was somewhat thicker and more porous than the film grown on the hills and smooth regions.This was due to the fact that the growth of the coating film was found to be localized in the presence of rough region,which was in line with the discharge activities.Herein,the nucleation and growth behavior during the initial stage of PEO will be discussed schematically on the basis of microstructural interpretation.