Identification of Active Hydrogen Species on Palladium Nanoparticles for an Enhanced Electrocatalytic Hydrodechlorination of 2,4-Dichlorophenol in Water.

Clarifying hydrogen evolution and identifying the active hydrogen species are crucial to the understanding of the electrocatalytic hydrodechlorination (EHDC) mechanism. Here, monodisperse palladium nanoparticles (Pd NPs) are used as a model catalyst to demonstrate the potential-dependent evolutions of three hydrogen species, including adsorbed atomic hydrogen (H*ads), absorbed atomic hydrogen (H*abs), and molecular hydrogen (H2) on Pd NPs, and then their effect on EHDC of 2,4-dichlorophenol (2,4-DCP). Our results show that H*ads, H*abs, and H2 all emerge at -0.65 V (vs Ag/AgCl) and have increased amounts at more negative potentials, except for H*ads that exhibits a reversed trend with the potential varying from -0.85 to -0.95 V. Overall, the concentrations of these three species evolve in an order of H*abs < H*ads < H2 in the potential range of -0.65 to -0.85 V, H*ads < H*abs < H2 in -0.85 to -1.00 V, and H*ads < H2 < H*abs in -1.00 to -1.10 V. By correlating the evolution of each hydrogen species with 2,4-DCP EHDC kinetics and efficiency, we find that H*ads is the active species, H*abs is inert, while H2 bubbles are detrimental to the EHDC reaction. Accordingly, for an efficient EHDC reaction, a moderate potential is desired to yield sufficient H*ads and limit H2 negative effect. Our work presents a systematic investigation on the reaction mechanism of EHDC on Pd catalysts, which should advance the application of EHDC technology in practical environmental remediation.