Title:
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New nanocatalysts made by bacteria from metal solutions and recycling of metal waste
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In this thesis, the bioconversion of palladium and gold solutions and gold-bearing wastes
into highly valuable mono- and bimetallic catalysts is described. This process relies on
bioreduction; the ability of some bacteria to reduce Pd(II) and Au(III) ions at the expense of
an exogenous electron donor with precipitation as zero valent metals. The resulting metallic
nanoparticles (NPs) immobilised on the outer membrane and within the periplasm exhibit
remarkable catalytic properties, sometimes surpassing commercially available catalyst
formulations in terms of activity and/or selectivity. Previous studies in the field have mainly
focused on the ability of Desulfovibrio spp. to reduce Pd(II) from both surrogate solutions and
reprocessing wastes. The mechanism of Pd(II) reduction in this genus was previously shown
to be enzymatic, involving hydrogenases, key enzymes of hydrogen metabolism. In this study,
a detailed investigation into the mechanism of Pd(II) reduction by Escherichia coli using a
genetic approach confirmed hydrogenase involvement and additionally showed that these
enzymes are needed to initiate the formation of Pd(O) nuclei. Genetically engineered strains
depleted of all functional hydrogenases lost their ability to produce Pd(O) NPs, which in turn
greatly affected the catalytic activity of the resulting bioinorganic catalyst ("bioPd(O)").
Further studies suggested that the nature of the bacterial support also influenced the catalytic
activity of bioPd(O) preparations. Seven bacterial strains, representing different Gramnegative
and Gram-positive genera, were tested for Pd(II) reduction. Large differences in
Pd(II) sorption and Pd(II) reduction ability were observed between strains; the combination of
these factors affected the final size distribution of the cell-bound Pd(O) NPs and hence the
catalytic activity of the resulting bioPd(O) preparations. Bioinorganic catalysts were shown to
be active and/or selective in a wide variety of reactions, including Cr(VI) reduction,
hydrogenolysis (reductive dehalogenation), Heck coupling and oxidations.
The bioreductive approach was applied to demonstrate Au(III) reduction and recovery
using cells of D. desulfuricans and E. coli and the first evidence of the catalytic activity of
biogenic Au(O) NPs is presented. Au(III) reduction was slower than Pd(II) reduction and only
partially involved hydrogenases which suggested the involvement of an additional different
reduction route. However, introducing a bionanocatalyst consisting of lightly pre-palladized
cells into the process greatly improved the speed of Au(III) reduction and resulted in the
formation of highly ordered AulPd core/shell nanostructures which exhibited catalytic
properties not seen with traditional chemical counterparts.
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