Synergetic Effect of Facet Junction and Specific Facet Activation of ZnFe₂O₄ Nanoparticles on Photocatalytic Activity Improvement

Crystal facet engineering has been proved as a versatile approach in modulating the photocatalytic activity of semiconductors. However, the facet-dependent properties and underlying mechanisms of spinel ZnFe2O4 in photocatalysis still have rarely been explored. Herein, ZnFe2O4 nanoparticles with different {001} and {111} facets exposed were successfully synthesized via a facile hydrothermal method. Facet-dependent photocatalytic degradation performance toward gaseous toluene under visible light irradiation was observed, where truncated octahedral ZnFe2O4 (ZFO(T)) nanoparticles with both {001} and {111} facets exposed exhibited a superior performance than the others. The formed surface facet junction between {010} and {100} facets was responsible for the improved activity by separating photogenerated e–/h+ pairs efficiently to reduce their recombination rate. Photogenerated electrons and holes were demonstrated to be immigrated onto {001} and {111} facets, separately. Intriguingly, electron paramagnetic resonance trapping results indicated that both •O2– and •OH were abundantly present in the ZFO(T) sample under visible light irradiation as major reactive oxygen species involved in the photocatalytic degradation process. Additionally, further investigation revealed that {001} facets played a predominant role in activating photogenerated transient species H2O2 into •OH, beneficially boosting the intrinsic photocatalytic activity. This work has not only presented a promising strategy in regulating photocatalytic performance through the synergetic effect of facet junction and specific facet activation but also broadened the application of facet engineering with multiple effects simultaneously cooperating.