Biosupported bimetallic Pd-Au nanocatalysts for dechlorination of environmental contaminants.

Biologically produced monometallic palladium nanoparticles (bio-Pd) have been shown to catalyze the dehalogenation of environmental contaminants, but fail to efficiently catalyze the degradation of other important recalcitrant halogenated compounds. This study represents the first report of biologically produced bimetallic Pd/Au nanoparticle catalysts. The obtained catalysts were tested for the dechlorination of diclofenac and trichlorethylene. When aqueous bivalent Pd(II) and trivalent Au(III) ions were both added to concentrations of 50 mg L(-1) and reduced simultaneously by Shewanella oneidensis in the presence of H(2), the resulting cell-associated bimetallic nanoparticles (bio-Pd/Au) were able to dehalogenate 78% of the initially added diclofenac after 24 h; in comparison, no dehalogenation was observed using monometallic bio-Pd or bio-Au. Other catalyst-synthesis strategies did not show improved dehalogenation of TCE and diclofenac compared with bio-Pd. Synchrotron-based X-ray diffraction, (scanning) transmission electron microscopy and energy dispersive X-ray spectroscopy indicated that the simultaneous reduction of Pd and Au supported on cells of S. oneidensis resulted in the formation of a unique bimetallic crystalline structure. This study demonstrates that the catalytic activity and functionality of possibly environmentally more benign biosupported Pd-catalysts can be improved by coprecipitation with Au.

Doping of biogenic Pd catalysts with Au enables dechlorination of diclofenac at environmental conditions.

By using the metal reducing capacities of bacteria, Pd nanoparticles can be produced in a sustainable way ('bio-Pd'). These bio-Pd nanoparticles can be used as a catalyst in, for example, dehalogenation reactions. However, some halogenated compounds are not efficiently degraded using a bio-Pd catalyst. This study shows that the activity of bio-Pd can be improved by doping with Au(0) ('bio-Pd/Au'). In contrast with bio-Pd, bio-Pd/Au could perform the removal of the model pharmaceutical compound diclofenac from an aqueous medium in batch experiments at neutral pH and with H(2) as the hydrogen donor (first order decay constant of 0.078 ± 0.009 h(-1)). Dehalogenation was for both catalysts the only observed reaction. For bio-Pd/Au, a disproportional increase of catalytic activity was observed with increasing Pd-content of the catalyst. In contrast, when varying the Au-content of the catalyst, a Pd/Au mass ratio of 50/1 showed the highest catalytic activity (first order decay value of 0.52 ± 0.02 h(-1)). The removal of 6.40 µg L(-1) diclofenac from a wastewater treatment plant effluent using bio-Pd was not possible even after prolonged reaction time. However, by using the most active bio-Pd/Au catalyst, 43.8 ± 0.5% of the initially present diclofenac could be removed after 24 h. This study shows that doping of bio-Pd nanoparticles with Au(0) can be a promising approach for the reductive treatment of wastewaters containing halogenated contaminants.