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

Abstract

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 (VO) 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 VO 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.