Chlorine-Coordinated Pd Single Atom Enhanced the Chlorine Resistance for Volatile Organic Compound Degradation: Mechanism Study

The development of catalysts with high chlorine resistance for volatile organic compound (VOC) degradation is of great significance to achieve air purification. Herein, Pd@ZrO₂ catalysts with monodispersed Pd atoms coordinated with Cl were prepared using an in situ grown Zr-based metal-organic framework (MOF) as the sacrifice templates to enhance the chlorine resistance for VOC elimination. The residual Cl species from the Zr-MOF coordinated with Pd, forming Pd₁-Cl species during the pyrolysis. Meanwhile, abundant oxygen vacancies (V_O) were generated, which enhanced the adsorption and activation of gaseous oxygen molecules, accelerating the degradation of VOCs. In addition, the Pd@ZrO₂ catalysts exhibited satisfactory water resistance, long-term stability, and great resistance to CO and dichloromethane (DCM) for VOC elimination. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results elucidated that the generation of Pd₁-Cl species in Pd@ZrO₂ suppressed the absorption of DCM, releasing more active sites for toluene and its intermediate adsorption. Simultaneously, the monodispersed Pd atoms and V_O improved the reactivity of gaseous oxygen molecule adsorption and dissociation, boosting the deep decomposition of toluene and its intermediates. This work may provide a new strategy for rationally designing high-chlorine resistance catalysts for VOC elimination to improve the atmospheric environment.