Beyond Nitrogen in the Oxygen Reduction Reaction on Nitrogen-Doped Carbons: A NEXAFS Investigation.

Polymer electrolyte membrane fuel cells require cheap and active electrocatalysts to drive the oxygen reduction reaction. Nitrogen-doped carbons have been extensively studied regarding their oxygen reduction reaction. The work at hand looks beyond the nitrogen chemistry and brings to light the role of oxygen. Nitrogen-doped nanocarbons were obtained by a radio-frequency plasma route at 0, 100, 250, and 350 W. The lateral size of the graphitic domain, determined from Raman spectroscopy, showed that the nitrogen plasma treatment decreased the crystallite size. Synchrotron radiation photoelectron spectroscopy showed a similar nitrogen chemistry, albeit the nitrogen concentration increased with the plasma power. Lateral crystallite size and several nitrogen moieties were plotted against the onset potential determined from oxygen reduction reaction curves. There was no correlation between the electrochemical activity and the sample structure, as determine from Raman and synchrotron radiation photoelectron spectroscopy. Near-edge X-ray absorption fine structure (NEXAFS) was performed to unravel the carbon and nitrogen local structure. A difference analysis of the NEXAFS spectra showed that the oxygen surrounding the pyridinic nitrogen was critical in achieving high onset potentials. The work shows that there were more factors at play, other than carbon organization and nitrogen chemistry.

Geochemical investigations of noble metal-bearing ores: Synchrotron-based micro-analyses and microcosm bioleaching studies.

Auriferous sulphide ores often incorporate micro-fine (or invisible) gold and silver particles in a manner making their extraction difficult. Nobel metals are lost in the tailings due to the refractory nature of these ores. Bioleaching is an environment-friendly alternative to the commonly used and toxic cyanidation protocols for gold extraction from refractory ores. In this paper, we investigate gold and silver bioleaching from porphyry and epithermal mineralisation systems, using iron-oxidizing bacteria Acidithiobacillus ferrooxidans. The invisible Au, sequestered in refractory ores, was characterised in situ by synchrotron micro X-Ray Fluorescence (SR-µ-XRF) and X-ray Absorption Spectroscopy (XAS), offering information on Au unaltered speciation at the atomistic level within the ore matrices and at a micro-scale spatial resolution. The SR-µ-XRF and XAS results showed that 10-20 µm sized elemental Au(0) nuggets are sequestered in pyrite, chalcopyrite, arsenopyrite matrices and at the interface of a mixture of pyrite and chalcopyrite. Moreover, the preliminary bioleaching experiments of the two types of ores, showed that Acidithiobacillus ferrooxidans can catalyse the dissolution of natural heterogeneous Fe-rich geo-matrices, sequestering Au and Ag and releasing particulate phases or partially solubilising them within 60 days. These results provide an understanding of noble metal sequestration and speciation within natural ores and a demonstration of the application of synchrotron-based micro-analysis in characterizing economic trace metals in major mineral structures. This work is a contribution to the ongoing efforts towards finding feasible and greener solutions of noble metal extraction protocols.

The effect and role of environmental conditions on magnetosome synthesis.

Magnetotactic bacteria (MTB) are considered the model species for the controlled biomineralization of magnetic Fe oxide (magnetite, Fe3O4) or Fe sulfide (greigite, Fe3S4) nanocrystals in living organisms. In MTB, magnetic minerals form as membrane-bound, single-magnetic domain crystals known as magnetosomes and the synthesis of magnetosomes by MTB is a highly controlled process at the genetic level. Magnetosome crystals reveal highest purity and highest quality magnetic properties and are therefore increasingly sought after as novel nanoparticulate biomaterials for industrial and medical applications. In addition, "magnetofossils," have been used as both past terrestrial and potential Martian life biosignature. However, until recently, the general belief was that the morphology of mature magnetite crystals formed by MTB was largely unaffected by environmental conditions. Here we review a series of studies that showed how changes in environmental factors such as temperature, pH, external Fe concentration, external magnetic fields, static or dynamic fluid conditions, and nutrient availability or concentrations can all affect the biomineralization of magnetite magnetosomes in MTB. The resulting variations in magnetic nanocrystals characteristics can have consequence both for their commercial value but also for their use as indicators for ancient life. In this paper we will review the recent findings regarding the influence of variable chemical and physical environmental control factors on the synthesis of magnetosome by MTB, and address the role of MTB in the global biogeochemical cycling of iron.

Cell division in magnetotactic bacteria splits magnetosome chain in half.

Cell division in magnetotactic bacteria has attracted much interest, speculation and hypothesis with respect to the biomineralised chains of magnetic iron-oxide particles known as magnetosomes. Here we report direct Transmission Electron Microscopy (TEM) evidence that division occurs at a central point of the cell and the chain, cleaving the magnetosome chain in two. Additionally, the new magnetosome chain relocates rapidly to the centre of the daughter cell and the number of magnetosomes is directly proportional to the cell length, even during the division part of the cell cycle.