Hydrogen storage in graphitic nanofibres

• Main Author: McCaldin, Simon Roger
• Published: University of Nottingham 2007
• Subjects: 662; TP Chemical technology
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.489972

There is huge need to develop an alternative to hydrocarbons fuel, which does not produce CO2 or contribute to global warming - 'the hydrogen economy' is such an alternative, however the storage of hydrogen is the key technical barrier that must be overcome. The potential of graphitic nanofibres (GNFs) to be used as materials to allow the solid-state storage of hydrogen has thus been investigated. This has been conducted with a view to further developing the understanding of the mechanism(s) of hydrogen storage in GNFs and modifying the material structure to maximise the amount of hydrogen that can be reversibly stored in the material. GNFs were synthesised using chemical vapour deposition (CVD) with careful control of temperature and gas mixture to create predominately herringbone GNFs from both Iron and Nickel catalysts. Within this, it was found that once GNF growth has been initiated under certain conditions, alteration of those conditions does not alter the fundamental structure of the GNF synthesised, but can increase the carbon yield, although reorientation of the surfaces was observed. The GNFs synthesised were subsequently chemically (acid washed and CO2 oxidised) and thermally treated to remove the residual CVD catalyst and alter their surface structures in an attempt to allow dihydrogen molecules to penetrate and adsorb onto the internal graphene layers. However, it was found that after initial growth, the surface layers of the GNFs became re-orientated parallel to the fibre axis - representing a large energy barrier to adsorption onto the surfaces of the internal graphene layers. By careful use and control of conditions, this re-orientated layer can be removed to yield GNFs with cleaned surfaces. Once GNFs with cleaned edges had been synthesised, these were modified to remove oxygen species from their surfaces. To further develop the understanding of the potential hydrogen uptake mechanisms, Pd particles were introduced to the GNF surfaces to act as catalyst gateways. By carefully controlling the variables of the incipient wetness process, a variety of morphologies and structures were synthesised. This allowed the precise determination of the hydrogen uptake mechanism occurring in samples by Kubas binding, Dissociation or Spill-over mechanisms. All of the GNFs created have had their hydrogen uptake capacities precisely determined using a Sieverts apparatus designed and constructed by the author. None of the samples were found to adsorb any significant levels of hydrogen (>0.1 wt%), regardless of the treatments applied to them – this result has been discussed in light of the existing claims for high hydrogen uptake in GNFs made within the literature. The conclusion of this thesis is that no hydrogen uptake capacity could be observed in the GNFs synthesised during the project, however, the development of the uptake mechanisms and GNF structures has led to suggested modifications that may yield GNFs suitable for storing large quantities of hydrogen (i.e. in excess of US-DOE targets).