Richard S. Cutting

Microbial engineering of nanoheterostructures: Biological synthesis of a magnetically recoverable palladium nanocatalyst

Precious metals supported on ferrimagnetic particles have a diverse range of uses in catalysis. However, fabrication using synthetic methods results in potentially high environmental and economic costs. Here we show a novel biotechnological route for the synthesis of a heterogeneous catalyst consisting of reactive palladium nanoparticles arrayed on a nanoscale biomagnetite support. The magnetic support was synthesized at ambient temperature by the Fe(III)-reducing bacterium, Geobacter sulfurreducens , and facilitated ease of recovery of the catalyst with superior performance due to reduced agglomeration (versus conventional colloidal Pd nanoparticles). Surface arrays of palladium nanoparticles were deposited on the nanomagnetite using a simple one-step method without the need to modify the biomineral surface, most likely due to an organic coating priming the surface for Pd adsorption, which was produced by the bacterial culture during the formation of the nanoparticles. A combination of EXAFS and XPS showed the Pd nanoparticles on the magnetite to be predominantly metallic in nature. The Pd(0)-biomagnetite was tested for catalytic activity in the Heck reaction coupling iodobenzene to ethyl acrylate or styrene. Rates of reaction were equal to or superior to those obtained with an equimolar amount of a commercial colloidal palladium catalyst, and near complete conversion to ethyl cinnamate or stilbene was achieved within 90 and 180 min, respectively.

Biomineralization: linking the fossil record to the production of high value functional materials

The microbial cell offers a highly efficient template for the formation of nanoparticles with interesting properties including high catalytic, magnetic and light-emitting activities. Thus biomineralization products are not only important in global biogeochemical cycles, but they also have considerable commercial potential, offering new methods for material synthesis that eliminate toxic organic solvents and minimize expensive high-temperature and pressure processing steps. In this review we describe a range of bacterial processes that can be harnessed to make precious metal catalysts from waste streams, ferrite spinels for biomedicine and catalysis, metal phosphates for environmental remediation and biomedical applications, and biogenic selenides for a range of optical devices. Recent molecular-scale studies have shown that the structure and properties of bionanominerals can be fine-tuned by subtle manipulations to the starting materials and to the genetic makeup of the cell. This review is dedicated to the late Terry Beveridge who contributed much to the field of biomineralization, and provided early models to rationalize the mechanisms of biomineral synthesis, including those of geological and commercial potential.

Bulk and key surface structures of hematite, magnetite, and goethite: A density functional theory study

Abstract The iron oxides hematite, magnetite, and goethite were studied with density functional theory to establish a consistent set of structures for both the bulk mineral and key surfaces, characterize surface relaxation, and predict and test calculated scanning tunneling microscopy (STM) images. Spinpolarized, plane-wave pseudopotential calculations were carried out on recognized terminations of the hematite (0001) and goethite (010) surfaces and on two terminations of magnetite (111), derived from bulk structures optimized with the same simulation parameters. In the bulk, geometry optimizations having different spin configurations were compared, to find that even without an on-site Coulomb correction, the expected spin states were found to have lowest energy: antiferromagnetic in hematite and goethite and ferrimagnetic in magnetite. However, magnetite shows a conducting minority spin. All four surfaces showed structural relaxation consistent with previous work. The ½-monolayer termination (octahedral and tetrahedral Fe) of magnetite (111) underwent slightly more relaxation than the ¼-monolayer termination, with consequently lower surface energy. A calculated STM image for ¼-monolayer magnetite is compared to an observed image at positive bias and suggests that the tetrahedral Fe dominates the image. STM images are predicted for hematite and goethite to aid interpretation of future experimental work.

Remediation of Cr(VI) by biogenic magnetic nanoparticles: An x-ray magnetic circular dichroism study

Remediation of Cr(VI) by biogenic magnetic nanoparticles: An x-ray magnetic circular dichroism study N. D. Telling 1 , V. S. Coker 1 , R. S. Cutting 1 , G. van der Laan 1,2 , C. I. Pearce 1 , R. A. D. Pattrick 1 , E. Arenholz 3 , and J. R. Lloyd 1 School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Manchester M13 9PL, UK Magnetic Spectroscopy Group, Diamond Light Source, Didcot, Oxfordshire, OX11 0DE, UK Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA Biologically synthesized magnetite (Fe 3 O 4 ) nanoparticles are studied using x-ray absorption and x-ray magnetic circular dichroism following exposure to hexavalent Cr solution. By examining their magnetic state, Cr cations are shown to exist in trivalent form on octahedral sites within the magnetite spinel surface. The possibility of reducing toxic Cr(VI) into a stable, non-toxic form, such as a Cr 3+ -spinel layer, makes biogenic magnetite nanoparticles an attractive candidate for Cr remediation. PACS number(s): 91.25.fa; 87.64.kd; 89.60.-k; 91.62.Rt

Microbial reduction of arsenic-doped schwertmannite by Geobacter sulfurreducens.

The fate of As(V) during microbial reduction by Geobacter sulfurreducens of Fe(III) in synthetic arsenic-bearing schwertmannites has been investigated. During incubation at pH7, the rate of biological Fe(III) reduction increased with increasing initial arsenic concentration. From schwertmannites with a relatively low arsenic content (<0.3 wt %), only magnetite was formed as a result of dissimilatory iron reduction. However, bioreduction of schwertmannites with higher initial arsenic concentrations (>0.79 wt %) resulted in the formation of goethite. At no stage during the bioreduction process did the concentration of arsenic in solution exceed 120 μgL(1), even for a schwertmannite with an initial arsenic content of 4.13 wt %. This suggests that the majority of the arsenic is retained in the biominerals or by sorption at the surfaces of newly formed nanoparticles. Subtle differences in the As K-edge XANES spectra obtained from biotransformation products are clearly related to the initial arsenic content of the schwertmannite starting materials. For products obtained from schwertmannites with higher initial As concentrations, one dominant population of As(V) species bonded to only two Fe atoms was evident. By contrast, schwertmannites with relatively low arsenic concentrations gave biotransformation products in which two distinctly different populations of As(V) persisted. The first is the dominant population described above, the second is a minority population characterized by As(V) bonded to four Fe atoms. Both XAS and XMCD evidence suggest that the latter form of arsenic is that taken into the tetrahedral sites of the magnetite. We conclude that the majority population of As(V) is sorbed to the surface of the biotransformation products, whereas the minority population comprises As(V) incorporated into the tetrahedral sites of the biomagnetite. This suggests that microbial reduction of highly bioavailable As(V)-bearing Fe(III) mineral does not necessarily result in the mobilization of the arsenic.

Cr(VI) and azo dye removal using a hollow-fibre membrane system functionalized with a biogenic Pd-magnetite catalyst

This study investigates the application of a hybrid system combining hollow-fibre membrane technology with the reductive abilities of magnetic nanoparticles for the remediation of toxic Cr(VI) and the azo dye, Remazol Black B. Nano-scale biogenic magnetite (Fe3O4), formed by microbial reduction of the mineral ferrihydrite, has a high reductive capacity due to the presence of Fe(II) in the mineral structure. The magnetic nanoparticles (∼ 20 nm) can be arrayed with Pd0 nanoparticles (∼ 5 nm) making a catalytically active nanomaterial. Membrane units, with and without nanoparticles, were challenged with either Cr(VI) or azo dye and some were supplemented with sodium formate, as an electron donor for contaminant reduction promoted by the Pd. The combination of Pd-magnetite with formate resulted in the most effective remediation strategy for both contaminants and the lifetime of the membrane unit was also increased, with 55% (19 days) and 70% (23 days) removal of the azo dye and Cr(VI), respectively. Low flow rates of 0.1 ml/min resulted in improved efficiencies due to increased contact time with the membrane/nanoparticle unit, with 70–75% removal of each contaminant. Chemical analyses of the nanoparticles post-exposure to Cr(VI) in the membrane modules indicated Pd to be more oxidized when Cr removal was maximized, and that the Cr was partially reduced to Cr(III) at the surface of the magnetite. These results have demonstrated that hollow-fibre membrane units can be enhanced for the removal of soluble, redox sensitive contaminants by incorporation of a layer of palladized biogenic nanoparticulate magnetite.