Electrochemical studies of diffusion in supercritical fluids

The challenges and specialised equipment associated with supercritical electrochemistry means standard reference electrodes (such as the saturated calomel electrode) cannot be used. The aim of the thesis is the investigation of a range of metallocenes as model redox systems against a Pt pseudo refer...

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Main Author: Branch, Jack Anthony
Other Authors: Bartlett, Philip
Published: University of Southampton 2015
Subjects:
540
Online Access:https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.655410
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spelling ndltd-bl.uk-oai-ethos.bl.uk-6554102018-09-05T03:22:48ZElectrochemical studies of diffusion in supercritical fluidsBranch, Jack AnthonyBartlett, Philip2015The challenges and specialised equipment associated with supercritical electrochemistry means standard reference electrodes (such as the saturated calomel electrode) cannot be used. The aim of the thesis is the investigation of a range of metallocenes as model redox systems against a Pt pseudo reference electrode in supercritical fluids. This work was then extended to the development of a new high pressure reactor. Initially, a range of metallocenes were investigated in liquid analogues of the supercritical fluids (acetonitrile and dichloromethane) to investigate their suitability. Cyclic voltammetry performed at both micro and macro electrodes were used to examine the behaviour of each individual redox couple. Electrochemistry of the metallocenes were then evaluated in supercritical fluids (supercritical carbon dioxide with acetonitrile and supercritical difluoromethane) for investigation as model redox systems. The diffusion coefficients have been determined at both micro and macro electrodes for both supercritical fluids. The implementation of baffled micro and macro electrodes has shown that the intrinsic convection (at the electrode surface) within supercritical fluids can be dampened. The diffusion of metallocenes in nanoporous aluminium oxide membranes (13 – 55 nm diameter cylindrical pores), in both supercritical fluids has also been investigated. This work was then extended to the development of a new high pressure plastic reactor leading to the first, successful, supercritical fluid electrodeposition of bismuth in the plastic reactor.540TP Chemical technologyUniversity of Southamptonhttps://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.655410https://eprints.soton.ac.uk/377597/Electronic Thesis or Dissertation
collection NDLTD
sources NDLTD
topic 540
TP Chemical technology
spellingShingle 540
TP Chemical technology
Branch, Jack Anthony
Electrochemical studies of diffusion in supercritical fluids
description The challenges and specialised equipment associated with supercritical electrochemistry means standard reference electrodes (such as the saturated calomel electrode) cannot be used. The aim of the thesis is the investigation of a range of metallocenes as model redox systems against a Pt pseudo reference electrode in supercritical fluids. This work was then extended to the development of a new high pressure reactor. Initially, a range of metallocenes were investigated in liquid analogues of the supercritical fluids (acetonitrile and dichloromethane) to investigate their suitability. Cyclic voltammetry performed at both micro and macro electrodes were used to examine the behaviour of each individual redox couple. Electrochemistry of the metallocenes were then evaluated in supercritical fluids (supercritical carbon dioxide with acetonitrile and supercritical difluoromethane) for investigation as model redox systems. The diffusion coefficients have been determined at both micro and macro electrodes for both supercritical fluids. The implementation of baffled micro and macro electrodes has shown that the intrinsic convection (at the electrode surface) within supercritical fluids can be dampened. The diffusion of metallocenes in nanoporous aluminium oxide membranes (13 – 55 nm diameter cylindrical pores), in both supercritical fluids has also been investigated. This work was then extended to the development of a new high pressure plastic reactor leading to the first, successful, supercritical fluid electrodeposition of bismuth in the plastic reactor.
author2 Bartlett, Philip
author_facet Bartlett, Philip
Branch, Jack Anthony
author Branch, Jack Anthony
author_sort Branch, Jack Anthony
title Electrochemical studies of diffusion in supercritical fluids
title_short Electrochemical studies of diffusion in supercritical fluids
title_full Electrochemical studies of diffusion in supercritical fluids
title_fullStr Electrochemical studies of diffusion in supercritical fluids
title_full_unstemmed Electrochemical studies of diffusion in supercritical fluids
title_sort electrochemical studies of diffusion in supercritical fluids
publisher University of Southampton
publishDate 2015
url https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.655410
work_keys_str_mv AT branchjackanthony electrochemicalstudiesofdiffusioninsupercriticalfluids
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