Novel Insight into the Synergistic Mechanism for Pd and Rh Promoting the Hydro-Defluorination of 4-Fluorophenol over Bimetallic Rh–Pd/C Catalysts

This study explores the synergistic effect between the Rh and Pd of bimetallic Rh–Pd/C catalysts for the catalytic hydro-defluorination (HDF) of 4-fluorophenol (4-FP). It was found that 4-FP could not be efficiently hydro-defluorinated over 6% Pd/C and 6% Rh/C due to the inherent properties of Pd and Rh species in the dissociation of H2 and the activation of C–F bonds. Compared with 6% Pd/C and 6% Rh/C, bimetallic Rh–Pd/C catalysts, especially 1% Rh–5% Pd/C, exhibited much higher catalytic activity in the HDF of 4-FP, suggesting that the synergistic effect between the Rh and Pd of the catalyst was much more positive. Catalyst characterizations (BET, XRD, TEM, and XPS) were introduced to clarify the mechanism for the synergistic effect between the Rh and Pd of the catalyst in the HDF reaction and revealed that it was mainly attributed to the bifunctional mechanism: Pd species were favorable for the dissociation of H2, and Rh species were beneficial to the activation of C–F bonds in the HDF reaction. Meanwhile, the interaction between Rh and Pd species enabled Rh and Pd to exhibit a more positive synergistic effect, which promoted the migration of atomic H* from Pd to Rh species and thus enhanced the HDF of 4-FP. Furthermore, 1% Rh–5% Pd/C prepared using 20–40 equiv NaBH4 exhibited the best performance in the catalytic HDF of 4-FP. Catalysis characterizations suggested that appropriate Rh3+/Rh0 and Pd2+/Pd0 ratios were beneficial to the dissociation of H2 and the activation of C–F bonds, which caused the more positive synergistic effect between the Rh and Pd of Rh–Pd/C in the HDF reaction. This work offers a valuable strategy for enhancing the performance of catalytic HDF catalysts via promoting synergistic effects.