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Hydrodechlorination of trichloroethylene over Pd supported on swellable organically-modified silica (SOMS)

2017-04-01
Sohn, Hyuntae
Çelik, Gökhan
Gunduz, Seval
Dean, Stacey L.
Painting, Eric
Edmiston, Paul L.
Ozkan, Umit S.
The catalytic activity and resistance to poisoning of Pd catalysts supported on swellable organically modified silica (SOMS) were investigated for hydrodechlorination (HDC) of trichloroethylene (TCE). The promising catalytic activity of 1% Pd/SOMS sample was attributed to the high affinity of SOMS for organics and its high hydrophobicity. While latter characteristic repels water, the adsorptive capacity for organics allows TCE dissolved in aqueous media to concentrate inside the pores, in the vicinity of the active sites, thus helping the kinetics. In the liquid phase, using a continuous flow reactor, higher TCE conversion was obtained over the 1% Pd/SOMS compared to the commercial 1% Pd/Al2O3 catalyst. When the pores of 1% Pd/SOMS sample were fully opened by pre-treating it with ethanol prior to the reaction, HDC activity was seen to significantly increase. In the gas phase, the extent of adsorption was less, reducing the concentration of reactants near the active sites. As a result, 1% Pd/SOMS was less active than 1% Pd/Al2O3 for HDC of TCE. To determine their resistance to poisoning, 1% Pd/SOMS and 1% Pd/A1203 catalysts were poisoned ex-situ with Li2S. The ex-situ poisoned Pd/SOMS sample maintained its catalytic activity for HDC of TCE. However, a significant loss in catalytic activity of the Pd/Al2O3 catalyst was observed after poisoning. Protection from aqueous phase sulfide poisoning was attributed to the hydrophobicity of the Pd/SOMS, which would exclude anionic species from the embedded Pd particles. The XPS, STEM and ICP-OES results indicated that when Pd/Al2O3 and Pd/SOMS were treated with 1 M HCI, most of the Pd metal was leached from the Pd/Al2O3 catalyst in contrast to Pd/SOMS, which had negligible leaching. Overall, due to hydrophobicity and high affinity for organics, SOMS has potential as a catalyst scaffold for different reactions in groundwater remediation applications.