Palladium Nanosheet Enables Synergistic Electrocatalytic Dehalogenation via Direct and Indirect Electron Transfer Mechanisms

Electrocatalytic dehalogenation is a promising method for the remediation of chlorinated organic pollutants. The dehalogenation performance is controlled by catalytic activity, and the underlying electrocatalytic dehalogenation mechanisms need to be carefully investigated for guiding the design of catalyst. Here we report the preparation of a new Pd-based catalyst with a nanosheet structure (Pd NS) by a simple wet-chemical reduction method. This Pd NS catalyst showed a superior electrocatalytic activity toward the reductive dehalogenation of a chlorinated organic pollutant (e.g., 4-chlorophenol) with the dehalogenation rate of 0.324 h^-1. Importantly, the obtained Pd NS catalyst had a good durability that could operate well over 30 h under high concentration of 4-chlorophenol with removal efficiency beyond 82%. Experimental results confirmed the simultaneous occurrence of direct electrocatalytic dehalogenation and H*-mediated indirect electron transfer mechanisms in the dehalogenation process, and their quantitative contributions to the dehalogenation performance were established based on the cyclic voltammetry and quenching experiments. This study provides a promising dehalogenation catalyst and sheds light on the mechanism of electrocatalytic dehalogenation as well as the development of a dual-functional electrocatalyst.