Modification of rutile titanium dioxide (TiO2) for hydrogen generation and water cleaning is a grand challenge due to the chemical inertness of rutile, while such inertness is a desired merit for its stability in photoelectrochemical applications. Herein, we report an innovative two-step method to prepare a core-shell nanostructured S-doped rutile TiO2 (R'-TiO2-S). This modified black rutile TiO2 sample exhibits remarkably enhanced absorption in visible and near-infrared regions and efficient charge separation and transport. As a result, the unique sulfide surface (TiO(2-x):S) boosts the photocatalytic water cleaning and water splitting with a steady solar hydrogen production rate of 0.258 mmol h(-1) g(-1). The black titania is also an excellent photoelectrochemical electrode exhibiting a high solar-to-hydrogen conversion efficiency of 1.67%. The sulfided surface shell is proved to be an effective strategy for enhancing solar light absorption and photoelectric conversion.
The nitrogenous nucleophile electrooxidation reaction (NOR) playsavital role in the degradation and transformation of available nitrogen. Focusing on the NOR mediated by the b-Ni(OH) 2 electrode,w ed ecipher the transformation mechanism of the nitrogenous nucleophile.F or the two-step NOR, proton-coupled electron transfer (PCET) is the bridge between electrocatalytic dehydrogenation from b-Ni(OH) 2 to b-Ni(OH)O,a nd the spontaneous nucleophile dehydrogenative oxidation reaction. This theory can give ag ood explanation for hydrazine and primary amine oxidation reactions,but is insufficient for the urea oxidation reaction (UOR). Through operando tracing of bond rupture and formation processes during the UOR, as well as theoretical calculations,wepropose apossible UOR mechanism whereby intramolecular coupling of the N À Nb ond, accompanied by PCET,hydration and rearrangement processes,results in high performance and ca. 100 %N 2 selectivity.T hese discoveries clarify the evolution of nitrogenous molecules during the NOR, and they elucidate fundamental aspects of electrocatalysis involving nitrogen-containing species.
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