O_(x)ygen vacancies on the BiOCl surface promoted photocatalytic complete NO oxidation via superoxide radicals

One of the core issues in the photocatalytic oxidation of nitric oxide is the effective co nversion of NO into the final product(nitrate).More than just improving the visible light photocatalytic performance of BiOCl,we aim to inhibit the generation of toxic by-product NO_(2) during this process.In this study,we demonstrate that the oxygen vacancies(OVs)modulate its surface photogene rated carrier transfer to inflect the NO conversion pathway by a facile mixed solvent method to induce OVs on the surface of BiOCl.The photocatalytic NO removal efficiency under visible light increased from 5.6%to 36.4%.In addition,the production rate of NO_(2) is effectively controlled.The effects of OVs on the generation of reactive oxygen species,electronic transfer,optical properties,and photocatalytic NO oxidation are investigated by combining density functional theory(DFT)theoretical calculations,the in situ FTIR spectra and experimental characterization.The OVs on the surface of BiOCl speed the trapping and transfer of localized electrons to activate the O_(2),producing O_(2)·,which avoid NO_(2) formation,resulting in complete oxidation of NO(NO+O_(2)·→NO_(3)).These findings can serve as the basis for controlling and blocking the generation of highly toxic intermediates through regulating the reactive species during the NO oxidation.It also can help us to understand the role of OV on the BiOCl surface and application of photocatalytic technology for safe air purification.

Honeycomb-like g-C_(3)N_(4)/CeO_(2)-x nanosheets obtained via one step hydrothermal-roasting for efficient and stable Cr(Ⅵ) photo-reduction

Graphitic carbon nitride(g-C_(3)N_(4))-based materials are regarded as one of the most potential photocatalysts for utilizing solar energy.In this work,we reported a facile one step in-situ hydrothermal-roasting method for preparing honeycomb-like g-C_(3)N_(4)/CeO_(2) nanosheets with abundant oxygen vacancies(g-C_(3)N_(4)/CeO_(2)-x).The hydrothermal-roasting and incomplete-sealed state can(i)generate an in-situ reducing atmosphere(CO,N2,NH3) to tune the concentration of oxygen vacancies in CeO_(2);(ii) beneficial to prevent continuous growth of g-C_(3)N_(4) and results in honeycomb-like g-C_(3)N_(4)/CeO_(2)-x hybrid nanosheets.What is more,the g-C_(3)N_(4)/CeO_(2)-x photocatalyst exhibited extended photoresponse range,increased specific surface area and obviously enhanced separation efficiency of photogenerated electron-hole pairs.As a proof-of-concept application,the optimized g-C_(3)N_(4)/CeO_(2)-xnanosheets could achieve 98% removal efficiency for Cr(Ⅵ) under visible light irradiation(λ≥420 nm)within 2.5 h,which is significantly better than those of pure g-C_(3)N_(4) and CeO_(2).This work provides a new idea for more rationally designing and constructing g-C_(3)N_(4)-based catalysts for efficient extended photochemical application.

New insight in the O_(2) activation by nano Fe/Cu bimetals:The synergistic role of Cu(0) and Fe(Ⅱ)

This study demonstrated that as-synthesized nano Fe/Cu bimetals could achieve significant enhancement in the degradation of diclofenac(DCF),as compared to much slow removal of DCF by Cu(Ⅱ) or zero valent iron nanoparticles(nZVI),respectively.Further observations on the evolution of O_(2) activation process by nano Fe/Cu bimetals was conducted stretching to the preparation phase(started by nZVI/Cu2+).Interesting breakpoints we re observed with obvious sudden increase in the DCF degradation efficiency and decrease in solution pH,as the original nZVI just consumed up to Fe(Ⅱ) and Cu(II) appeared again.It suggested that the four-electrons reaction of O_(2) and Cu-deposited nZVI would occur to generate water prior to the breakpoints,while Cu(0) and Fe(Ⅱ) would play most important role in activation of O_(2) afterwards.Through the electron spin resonance(ESR) analysis and quenching experiments.·OH was identified as the responsible reactive species.Further time-dependent quantifications in the cases of Cu(0)/Fe(Ⅱ) systems we re carried out.It was found that the ’OH accumulation was positively and linearly correlated with nCu dose,Fe(Ⅱ) consumption,and Fe(II) dose,respectively.Since either Cu(O) or Fe(Ⅱ)would be inefficient in activating oxygen to produce ·OH,a stage-evolution mechanism of O_(2) activated by nano Fe/Cu bimetals was proposed involving:(a) Rapid consumption of Fe(0) and release of Fe(Ⅱ) based on the Cu-Fe galvanic corrosion,(b) adsorption and transformation of O_(2) to O_(2)2 at the nCu surface,and(c) Fe(Ⅱ)-catalyzed activation of the adsorbed O_(2)2 to ·OH.