Alumina‐Supported Ni–Au: Surface Synergistic Effects in Catalytic Hydrodechlorination

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Abstract
Catalytic gas‐phase hydrodechlorination (HDC) of 2,4‐dichlorophenol (2,4‐DCP) has been investigated over Ni/Al2O3 and Au/Al2O3 prepared by impregnation, and Au–Ni/Al2O3 prepared by reductive deposition of Au onto Ni. Catalyst activation by temperature‐programmed reduction is examined and the activated catalysts are characterized in terms of H2 chemisorption, XRD and TEM‐energy dispersive X‐ray (EDX) measurements. Ni/Al2O3 (2O3 (2O3 bore larger particles (1–30 nm) with variable surface Ni/Au ratios. Au/Al2O3 exhibits low H2 uptake and low HDC activity to generate 2‐chlorophenol (2‐CP) as the sole product. H2 chemisorption on Au–Ni/Al2O3 was approximately five times lower than that recorded for Ni/Al2O3 but both catalysts delivered equivalent initial HDC activities. Ni/Al2O3 exhibits an irreversible temporal deactivation where partial dechlorination to 2‐CP is increasingly favored over full dechlorination to phenol. In contrast, thermal treatment of Au–Ni/Al2O3 in H2 after reaction elevates HDC activity with a preferential full HDC to phenol. This response is linked to a surface reconstruction resulting in a more homogeneous combination of Ni and Au. This result was also achieved by a direct treatment of Au–Ni/Al2O3 with HCl. A parallel/ consecutive kinetic model is used to quantify the catalytic HDC response.

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