Biomanufacture of nano-Pd(0) by Escherichia coli and electrochemical activity of bio-Pd(0) made at the expense of H2 and formate as electron donors.

OBJECTIVE: Palladised cells of Desulfovibrio desulfuricans and Shewanella oneidensis have been reported as fuel cell electrocatalysts but growth at scale may be unattractive/costly; we have evaluated the potential of using E. coli, using H2/formate for Pd-nanoparticle manufacture. RESULTS: Using 'bio-Pd' made under H2 (20 wt%) cyclic voltammograms suggested electrochemical activity of bio-NPs in a native state, attributed to proton adsorption/desorption. Bio-Pd prepared using formate as the electron donor gave smaller, well separated NPs; this material showed no electrochemical properties, and hence little potential for fuel cell use using a simple preparation technique. Bio-Pd on S. oneidensis gave similar results to those obtained using E. coli. CONCLUSION: Bio-Pd is sufficiently conductive to make an E. coli-derived electrochemically active material on intact, unprocessed bacterial cells if prepared at the expense of H2, showing potential for fuel cell applications using a simple one-step preparation method.

Configuration of microbially synthesized Pd-Au nanoparticles studied by STEM-based techniques.

Bimetallic Pd-Au particles synthesized using Desulfovibrio desulfuricans bacteria are characterized using scanning transmission electron microscopy (STEM) with a high-angle annular dark field (HAADF) detector combined with energy dispersive x-ray (EDX) silicon drift detector (SDD) elemental mapping and plasmon electron energy-loss spectroscopy (EELS). When combined with EDX, theoretical considerations or EELS, the atomic-number contrast (Z-contrast) provided by HAADF-STEM is effective in characterizing the compositional configuration of the bimetallic nanoparticles. Homogeneous mixing and complex segregations have been found for different particles in this work. The EELS study has also found different behaviours corresponding to surface plasmon resonances in different regions of a single particle due to its heterogeneity and anisotropy. HAADF-STEM tomography has been performed to obtain three-dimensional (3D) visualization of the nanoparticles.

Versatility of a new bioinorganic catalyst: palladized cells of Desulfovibrio desulfuricans and application to dehalogenation of flame retardant materials.

The versatility and reaction specificity of a novel bioinorganic catalyst is demonstrated in various reactions. Palladized cells (bioPd) of the sulphate-reducing bacterium Desulfovibrio desulfuricans showed an increased product selectivity and a catalytic activity comparable to a commercial Pd catalyst in several industrially relevant hydrogenations and hydrogenolyses (reductive dehalogenations). The ability of palladized cells to promote the reductive debromination of a polybrominated diphenyl ether (PBDE #47) is demonstrated, although chemically reduced Pd(II) and commercial Pd(0) were more effective debromination agents. Polybrominated diphenyl ethers are being supplanted as flame retardants by other compounds, e.g. tris(chloroisopropyl)phosphate (TCPP), the concentration of which was seen to increase approximately 10-fold in groundwater samples between 2000 and 2004. BioPd dechlorinated TCPP in groundwater samples with >90% recovery of free chloride ion, and was five times more effective than using commercial Pd(0) catalyst. Examination of the spent groundwater using 31P NMR showed a phosphorus species novel to the bioPd-treated solution, which was not evident in a commercial reference sample of TCPP.

Biorecovery of gold by Escherichia coli and Desulfovibrio desulfuricans.

Microbial precipitation of gold was achieved using Escherichia coli and Desulfovibrio desulfuricans provided with H2 as the electron donor. No precipitation was observed using H2 alone or with heat-killed cells. Reduction of aqueous AuIII ions by both strains was demonstrated at pH 7 using 2 mM HAuCl4 solution and the concept was successfully applied to recover 100% of the gold from acidic leachate (115 ppm of AuIII) obtained from jewelry waste. Bioreductive recovery of gold from aqueous solution was achieved within 2 h, giving crystalline Au0 particles (20-50 nm), in the periplasmic space and on the cell surface, and small intracellular nanoparticles. The nanoparticle size was smaller (red suspension) at acidic pH (2.0) as compared to that obtained at pH 6.0 and 7.0 (purple) and 9.0 (dark blue). Comparable nanoparticles were obtained from AuIII test solutions and jewelry leachate.