Modification of Pd Nanoparticles with Lower Work Function Elements for Enhanced Formic Acid Dehydrogenation and...

Catalytic degradation of halogenated contaminants by palladium (Pd) is a promising technology for environmental remediation. However, the low utilization of H by Pd catalyst and its easy poisoning prevent its applications. Here, low work function elements (B or Ag) were incorporated into Fe@C-supported Pd nanoparticles (NPs) to alter their crystalline structure and induce electronic effects, addressing these issues. The Pd mass-normalized dechlorination rates of trichloroethylene (TCE) by Fe@C-Pd-B and Fe@C-Pd-Ag were 51 and 59 times higher than that of unmodified Fe@C-Pd, respectively. The H utilization efficiency of Fe@C-Pd-B and Fe@C-Pd-Ag was 5.4 and 7.2 times higher than that of unmodified Fe@C-Pd, respectively. Various characterizations suggest that the B or Ag incorporation induced the charge redistribution and elevated the electron density of Pd atoms, resulting in the enhanced formic acid (FA) dehydrogenation and TCE dechlorination. Although the Ag incorporation presented a relatively higher H utilization due to the suppressed combination of H and accumulation of unsaturated hydrocarbons (i.e., C₂H₄), the Fe@C-Pd-Ag was easily deactivated. In contrast, the B incorporation enabled the Pd NPs with a good stability. These findings can guide the rational design of robust Pd-based catalysts for efficient and selective FA dehydrogenation and chlorinated contaminant degradation.