Phase‐Controlled Pd─S Nanosheet Aerogels for Electrocatalytic Upgrading of Waste Plastics

Abstract Phase engineering of metal sulfides offers a promising strategy to enhance the catalytic performance by adjusting their atomic arrangement and electronic structure. However, achieving continuous phase‐controlled metal sulfides and elucidating the structure‐performance relationship remains a significant challenge. Herein, for the first time, a novel class of phase‐controlled palladium‐sulphur nanosheet aerogels (Pd─S NAs) aimed at enhancing electrocatalytic waste polymer‐derived ethylene glycol oxidation reaction (EGOR) is introduced. Remarkably, benefiting from the ordered atomic arrangement, Pd₃S NAs with Pd₄S phase deliver superior electrocatalytic performance toward EGOR, surpassing both S‐doped Pd NAs (Pd₉S NAs) and amorphous Pd₁S NAs. Density functional theory calculations reveal that the different phase is a vital structural descriptor for performance, where ordered phase structure is the intrinsic contribution to the excellent performance of Pd₃S NAs. Compared with other Pd─S NAs, Pd₃S NAs have regular atomic arrangements, which promote the oxidation of carbon monoxide intermediate (^*CO), cause optimal adsorption of the CH₂OHCOO^* key intermediates during EGOR, facilitate selective EG oxidation to glycolic acid, and lower the reaction barrier in the potential determining step of the reaction, thus presenting the excellent EGOR performance. This study advances the phase‐controlled synthesis of Pd‐based nanomaterials and highlights the importance of phase‐dependent catalytic properties in electrocatalysis.