University of St Andrews

Project description

Solid oxide fuel cells offer the most efficient method for conversion of biofuels to electrical energy; however, there a number of important considerations. First of all coking of fuel must be avoided and second it is important to maximise the electrical conversion efficiency, especially in the Brazilian context where heat is not generally a useful byproduct. In this project, we will consider fuels such as bioethanol, bioglycerol and bio-oils applying autothermal reforming strategies to optimise electrical output. A range of metallic and oxide composite anodes, maintaining low contents of coking active species such as Ni, will be investigated. Work will entail both heterogeneous catalytic studies, addressing thermal signature of reforming/oxidation processes and electrochemical tests of prospective anodes in realistic fuel streams.

Availability

Co-tutelle PhD (12 months UK, 24 in Brazil)

Supervisers

• University of St Andrews Supervisor(s):

  Prof. John TS Irvine (School of Chemistry, St Andrews)

• Brazilian University Supervisor(s):

  Dr Fabio Coral Fonseca, Dr. Marcelo Linardi, IPEN/CNEN-SP, Programa Célula a Combustível. Av. Lineu Prestes 2242, Cidade Universitária, São Paulo (SP), Brasil 05508-000

Additional notes

The groups interacted at the European SOFC Forum at Lucerne in 2010 that Irvine chaired. St Andrews interests in direct hydrocarbon fuel cells are closely correlated with Brazilian Technical priorities. Relevant publications: [1] "Advanced Anodes for High-Temperature Fuel Cells", A. Atkinson , S Barnett, R.J. Gorte, J.T.S. Irvine , A.J. McEvoy, M. Mogensen, C. Singhal , J.Vohs, Nature Materials, 2004, 3, 17-27. [2] "A Redox-Stable, Efficient Anode For Solid-Oxide Fuel Cells", S Tao and JTS Irvine, Nature Materials, 2003, 2, 320-323.

Start date

September 2012 or February 2013

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Project description

Hydrocarbon assessment in Palaeozoic basins often is guided by thermal histories estimated using the conodont alteration index (CAI), in which colour of protein-associated, nano-scale carbonate-apatite crystallites changes systematically as a function of peak temperature and the duration of time over which that temperature persisted. Reflectivity of collagenous graptolite fossils (Graptolite Reflectivity) is used in a similar way to vitrinite reflectance at younger ages, again to estimate maximum burial temperature, although time effects are considered less important and material properties more influential for the GR index than for CAI. Both indices are estimated manually, by microscopic comparison to standards and to the empirical database of similar measurements globally. This yields thermal maturity estimates graded in successive bins spanning ~30-50 °C (i.e., “70-100 °C “; 100-150 °C”, “150-200 °C”). These discrete temperature bins and strong time-dependence (for CAI) are major functional shortcomings of the indices. Furthermore, bedding-focused fluid flow and matrix-/material- properties of the fossils and the rocks hosting them are known to have potentially strong, though as-yet uncalibrated influences. Modern mineralogic spectroscopic methods are capable of quantifying conodont colour, graptolite reflectance, and matrix petrographic textural maturity in rich detail. The PhD student will spectroscopically characterize conodonts and graptolites from black shales crossing thermal gradients from immature, into the oil and gas windows, then past thermal cracking to supermature, anchizone, and greenschist metamorphic grade. Similar characterization will be performed on industry standard and in-laboratory experimental alteration series, and specific successions with independent evidence for assessing fluid flow and material-/matrix-effects. Reference monitor samples will be cross-correlated against other indices for thermal maturity, such as illite and chlorite crystallinity, H-, C-, and O- pyrolysis indices, and biomarker ratios, i.e. even/odd long-chain hydrocarbons.

Availability

Full PhD (36 months in UK)

Supervisers

• University of St Andrews Supervisor(s):

  Dr Timothy Raub, Department of Earth Sciences

• Brazilian University Supervisor(s):

  n/a

Additional notes

The project is intended to introduce analytical rigour to methods used ubiquitously in the petroleum- and natural gas industries, and to significantly reduce analysis time. These data also are of academic importance for a variety of basin- and tectonic-modeling, and palaeo-geochemistry studies.

Start date

September 2012 or February 2013

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Project description

Although bacterial precipitation of and incorporation into carbonate rocks is relatively rare on Earth today, it has dominated older ages of Earth history, including episodes of unprecedented global carbon cycle change and climate response in the late Precambrian, the Palaeozoic, and the Cretaceous-Palaeogene. Some of these microbial carbonates are structured into stromatolitic bioherms; and they may be either dominated by limestone or by dolostone composition. Primary porosity and later hydrocarbon permeability networks are influenced by these depositional differences as well as variable behavior upon diagenesis and burial dewatering. Thus understanding the chemostratigraphy and the inherent geochemical systematics of microbial carbonates is of first-order importance both for understanding Earth history and fthe distribution and beneficiation of hydrocarbon resources. The PhD student will undertake extensive fieldwork in South Australia, one of the few places on Earth where modern dolomite and magnesite are precipitating in microbial-influenced estuaries of the Coorong; and where an exceptional record of microbial carbonate deposition in the Adelaidean Torrensian and Willouran Series is preserved across the ~800 Ma “Bitter Springs Event”, one of the most enigmatic and striking excursions to Earth’s geologic carbon cycle anywhere in the rock record. Methods employed will include water and rock isotope geochemistry of inorganic and organic carbon, oxygen, and sulphur. Sedimentary texture and sequence stratigraphic analysis also will be employed.

Availability

Full PhD (36 months in UK)

Supervisers

• University of St Andrews Supervisor(s):

  Dr Timothy Raub, Dr Tony Prave,

• Brazilian University Supervisor(s):

  n/a

Additional notes

Results will be tailored for presentation both to targeted audiences in the hydrocarbon industry and in the academic Earth History community.

Start date

September 2012 or February 2013

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Project description

The use of bimetallic nanoparticles supported on oxides is widespread in industrial catalysis. It is extremely important to characterise the elemental distribution within bimetallic nanoparticles as functions of temperature and gas environment since optimising and maintaining selectivity in complex catalytic processes requires well-defined surface atomic arrangements. Baddeley is expert in the use of medium energy ion scattering (MEIS) to characterise the depth dependent composition of bimetallic surfaces. Grande and co-workers have developed an elegant and sophisticated method to analyse MEIS data from sub-5nm nanoparticles arising from a detailed understanding of the asymmetrical energy-loss line shape in MEIS spectra.

Availability

Co-tutelle PhD (12 months UK, 24 in Brazil)

Supervisers

• University of St Andrews Supervisor(s):

  Dr Chris J. Baddeley (School of Chemistry, St Andrews),

• Brazilian University Supervisor(s):

  Prof Pedro L. Grande (Instituto de Física, Universidade Federal do Rio Grande do Sul, Avenida Bento Gonçalves 9500, 91501-970 Porto Alegre, Rio Grande do Sul, Brazil)

Additional notes

Student will spend time optimising sample preparation in St Andrews and acquiring data at the new MEIS facility at the University of Huddersfield. Detailed analysis of data will be carried out in Porto Alegre.[1] M.A. Sortica, P.L. Grande, G. Machado, L. Miotti, J. Appl. Phys. 106 (2009) 114320; [2] A.R. Haire, J. Gustafson, A.G. Trant, T.E. Jones, T.C.Q. Noakes, P. Bailey, C.J. Baddeley, Surf. Sci. 605 (2011) 214;[3] J. Gustafson, A.R. Haire, C.J. Baddeley, Surf. Sci. 605 (2011) 220.

Start date

September 2012 or February 2013

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Project description

We propose to prepare multiply-doped ceria nanomaterials for application in new anode catalysts and electrolyte materials for intermediate temperature Solid Oxide Fuel Cells using hydrocarbon and bioethanol fuels. Anodes and electrolytes will require very different starting morphologies and doping strategies and we have experience in this area. [1-5] Key to both materials sets is the dependence of their defect chemistry and precise crystallography on temperature and gas atmosphere. Redox, catalytic and electrochemical evaluation at St Andrews will be coupled with in situ crystallography and X-ray absorption spectroscopy in Brazil in order to relate macroscopic performance to atomic environment and oxidation state.

Availability

Co-tutelle PhD (12 months UK, 24 in Brazil)

Supervisers

• University of St Andrews Supervisor(s):

  Dr Richard T. Baker (School of Chemistry, St Andrews),

• Brazilian University Supervisor(s):

  Dr Marcia Carvalho de Abreu Fantini (Instituto de Física da Universidade de São Paulo, Rua do Matão Travessa R Nr.187 CEP 05508-090 Cidade Universitária, São Paulo - Brasil).

Additional notes

Dr^a Fantini and Baker and Fuentes co-authored a paper [6] on the reduction behaviour of ZrO₂-CeO₂ solid solutions with tubular nanostructure. Dr^a Fantini is Head of Department, has published over 100 papers and is an expert on the application of X-ray diffraction, X-ray scattering and X-ray absorption spectroscopy (XRD, SAXS, EXAFS) to the study of materials including highly porous oxides and nanostructured zirconia. Her group is a frequent user of the Brazilian Laboratory of Synchrotron Light (LNLS). As part of a long-standing collaboration, Baker and Fuentes (previously a Postdoctoral Research Fellow in the Baker group, now group leader at Dept. of Condensed Matter Physics, National Committee for Atomic Energy, Buenos Aires, Argentina) have ten joint papers on ceria-based materials for fuel cell applications. They have made use of the XRD, XANES and EXAFS capabilities at the LNLS on several occasions to study the redox behaviour and crystallography of nanostructured doped cerium oxide materials and Dr Fuentes is a very experienced user of the LNLS. Baker speaks, reads and writes Portuguese having worked in the language for two years at the University of Aveiro, Portugal. References: [1] R.O. Fuentes, R.T. Baker, J. Power Sources 184 (2009) 268. [2] R.O. Fuentes and R.T. Baker. J. Phys. Chem. C 113 (2009) 914. [3] S. Song, R.O. Fuentes, R.T. Baker. J. Mater. Chem. 20 (2010) 9760.

Start date

September 2012 or February 2013

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Project description

Nanomaterials based on doped ceria and other compositions will be prepared and evaluated for application in new anode catalysts and electrolyte materials for Solid Oxide Fuel Cells. Anodes and electrolytes will require very different starting morphologies and doping strategies and we have experience in this area. [1-5] The excellent facilities for electron microscopy (SEM and HRTEM, both with EDX analysis) and XRD at St Andrews will be used to characterise the starting powders. Novel redox and catalytic methods will be used to identify the best compositions and these will be incorporated into electrochemical cells for evaluation as working fuel cell components.

Availability

Full PhD (36 months in UK)

Supervisers

• University of St Andrews Supervisor(s):

  Dr Richard T. Baker (School of Chemistry, St Andrews)

• Brazilian University Supervisor(s):

  n/a

Additional notes

Dr. Baker speaks, reads and writes Portuguese having worked in the language for two years at the University of Aveiro, Portugal. References: [1] R.O. Fuentes, R.T. Baker, J. Power Sources 184 (2009) 268. [2] R.O. Fuentes and R.T. Baker. J. Phys. Chem. C 113 (2009) 914. [3] S. Song, R.O. Fuentes, R.T. Baker. J. Mater. Chem. 20 (2010) 9760. [4] M.R. Kosinski, R.T. Baker, J. Power Sources, 196 (2011) 2498. [5] J. Kearney, J.C. Hernández-Reta, R.T. Baker, Catal. Today (2012) 139.

Start date

September 2012 or February 2013

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