Mechanism in chlorine-enhanced Pd catalyst for H2O2 in situ synthesis in electro-Fenton system

Palladium-based catalysts have been widely employed in the electro-Fenton process for in situ generation of H2O2. However, the process is still far from being practical on a large scale. In this work, a series of ClxFePd/gamma-Al2O3/Al catalysts were prepared by a three-step-impregnation method. They exhibited excellent activity in H2O2 in situ synthesis and high efficiency in phenol degradation. The characterization results showed that Cl could assist in increasing the content of Pd-0 and reducing the isoelectric point of catalysts, which led to the drastic promotion in the synthesis of H2O2. Theoretical calculations further demonstrated that Cl doping could facilitate the main reaction in H2O2 synthesis, as well as inhibit side reactions such as dissociation of the O-O bond. Furthermore, kinetic models were proposed and fitted. A plausible reaction mechanism as well as degradation pathways were elaborated based on electron spin resonance and gas chromatography-mass spectrometry results. These findings illustrate the value of palladium-based ClxFePd/gamma-Al2O3/Al catalysts for their application in the electro-Fenton process.