Hydrodechlorination of chlorophenols over Pd catalysts supported on zeolite Y, MCM-41 and graphene

Hydrodechlorination (HDC) reaction of chlorophenols was carried out using Pd catalysts supported over zeolite Y, MCM-41 or graphene. Pd-MCM-41 and Pd-Y zeolite were prepared by impregnation and ion-exchange method, respectively. Pd-graphene (Pd-G) was prepared by hydrazine hydrate reduction of palladium ion dispersed on graphene oxide. The catalysts were characterized by several analytical tools such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). These catalysts were subjected to HDC reaction of chlorophenols, such as 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP) and 3,4-dichlorophenol (3,4-DCP). The reaction rate of HDC of chlorophenols catalyzed by Pd catalysts with various solid bases, such as KF/Al 2 O 3 (alumina), sodium acetate (NaOAc) and K 2 CO 3 was compared. First, Pd-MCM-41 and Pd-Y catalysts were compared. 2,4- and 3,4-DCPs were completely decomposed within 6 h, in the case of Pd-MCM-41 with NaOAc. Using Pd-Y instead of Pd-MCM-41 with NaOAc, much faster decomposition was observed. Faster decomposition of 4-CP and DCPs was observed with NaOAc base than K 2 CO 3 or KF/Al 2 O 3 under the same condition. In the case of Pd-Y with KF/Al 2 O 3 , slower decomposition of 4-CP and DCPs was observed. These base effects were interpreted using the solubility of NaCl and KCl in alcohol and the basic sites of KF/Al 2 O 3 . Because the solubility of NaCl is known to be larger than KCl solubility in alcohol, byproduct NaCl could be easily dissolved and ionized in solvents. For Pd-Y with KF/Al 2 O 3 , the small pore size of Y zeolite can interfere with the diffusion of HCl to KF/Al 2 O 3 basic site. Second, three catalysts, including Pd-graphene, were compared. 2,4-DCP was decomposed within 2 h using Pd-G with either K 2 CO 3 , NaOAc or KF/Al 2 O 3 . Pd-G catalyst showed the highest catalytic activity among Pd-G, Pd-MCM-41 and Pd-Y catalysts. The high activity and stability of the Pd-G could be attributed to the strong metal–support interaction with an electron-deficient site and a critical Pd particle size (ca. 3.5 nm) of Pd-G nanocatalyst with a stronger resistance to the deactivation and good affinity toward aromatic organic molecules, especially phenols. The progress of HDC reaction was monitored by gas chromatography with flame ionization detection (GC/FID), and a feasible degradation process could be explained by analy