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Synthesis of phthalocyanines for dye sensitized solar cells and stabilised pigment systems. / Sarah Rugen-Hankey

Swansea University Author: Sarah Rugen-Hankey

Abstract

This thesis reports the synthesis of novel phthalocyanine based photosensitizers for DSSC devices. Key precursors, halogenated phthalonitriles have been synthesised and characterised, which included a novel periodic acid method for forming 4,5-diiodophthalonitrile. Phthalonitrile derivatives with fu...

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Published: 2010
Institution: Swansea University
Degree level: Doctoral
Degree name: EngD
URI: https://cronfa.swan.ac.uk/Record/cronfa42591
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spelling 2018-08-02T16:24:29.7745958 v2 42591 2018-08-02 Synthesis of phthalocyanines for dye sensitized solar cells and stabilised pigment systems. 85981f4ab8d6582823d5bc31d2a92aa2 NULL Sarah Rugen-Hankey Sarah Rugen-Hankey true true 2018-08-02 This thesis reports the synthesis of novel phthalocyanine based photosensitizers for DSSC devices. Key precursors, halogenated phthalonitriles have been synthesised and characterised, which included a novel periodic acid method for forming 4,5-diiodophthalonitrile. Phthalonitrile derivatives with functionalities were synthesised from halogenated phthalonitriles via palladium cross coupling reactions. A novel fumaronitrile anchoring group was synthesised from commercially available methyl 4-(cyanomethyl)-benzoate along with the literature compound 4,5-bis(4-methoxycarbonylphenyl) phthalonitrile. Negishi coupling of 1,1'-dibromo- and ethynylerrocene compounds to halogenated phthalonitriles are also described and characterised along with the synthesis of the solubilising group nonoxyphthalonitrile. The effectiveness of the subphthalocyanine and statistical cyclotetramisation routes to phthalocyanine synthesis using the substituted phthalonitiles has been investigated in the preparation of substituted azapoiphyrines and unsymmetrical phthalocyanines. The dyes contained different donor (r-butyl and nonoxy) and acceptor (carboxylic acid) functional groups, especially designed for sensitisation in DSSC devices. Ring expansion reaction of the subphthalocyanines was very dependent on the substituent and reaction conditions and, in many cases, was not a selective process. Statistical cyclotetramisation of mixed substituted phthalonitriles formed pseudo statistical mixtures where it proved hard to separate the individual compounds from each other. Both the substituted azaporphyrines and unsymmetrical phthalocyanine dyes were used to sensitise naonparticular titiania and constructed into DSSC devices, in which IV and IPCE curves have been measured for each dye. DSSC photoactivity was observed for each unsymmetrical substituted dye. This thesis also describes the synthesis and characterisation of magnesium-aluminium layered double hydroxide clays which, in turn, were used in the preparation of phthalocyanine-suppoited and phthalocyanine-intercalated layered double hydroxides. These substituted clays were then used for the preparation of stabilised pigment systems and were incorporated into model paint formulations based on a PVC matrix. Degradation studies were earned out using the CO2 Flat Panel Reactor using UV irradiated panels coated with the paint formulations. The effect of clay particle morphology, clay particle size, clay-pigment preparation method and pigment loading concentration were all investigated with results showing that > 5 % pigment loading was required to reduce PVC degradation rates. Reflectance measurements were also used to monitor degradation of the panels. E-Thesis Materials science. 31 12 2010 2010-12-31 COLLEGE NANME Engineering COLLEGE CODE Swansea University Doctoral EngD 2018-08-02T16:24:29.7745958 2018-08-02T16:24:29.7745958 Faculty of Science and Engineering School of Engineering and Applied Sciences - Uncategorised Sarah Rugen-Hankey NULL 1 0042591-02082018162506.pdf 10805349.pdf 2018-08-02T16:25:06.5300000 Output 16811347 application/pdf E-Thesis true 2018-08-02T16:25:06.5300000 false
title Synthesis of phthalocyanines for dye sensitized solar cells and stabilised pigment systems.
spellingShingle Synthesis of phthalocyanines for dye sensitized solar cells and stabilised pigment systems.
Sarah Rugen-Hankey
title_short Synthesis of phthalocyanines for dye sensitized solar cells and stabilised pigment systems.
title_full Synthesis of phthalocyanines for dye sensitized solar cells and stabilised pigment systems.
title_fullStr Synthesis of phthalocyanines for dye sensitized solar cells and stabilised pigment systems.
title_full_unstemmed Synthesis of phthalocyanines for dye sensitized solar cells and stabilised pigment systems.
title_sort Synthesis of phthalocyanines for dye sensitized solar cells and stabilised pigment systems.
author_id_str_mv 85981f4ab8d6582823d5bc31d2a92aa2
author_id_fullname_str_mv 85981f4ab8d6582823d5bc31d2a92aa2_***_Sarah Rugen-Hankey
author Sarah Rugen-Hankey
author2 Sarah Rugen-Hankey
format E-Thesis
publishDate 2010
institution Swansea University
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Uncategorised{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Uncategorised
document_store_str 1
active_str 0
description This thesis reports the synthesis of novel phthalocyanine based photosensitizers for DSSC devices. Key precursors, halogenated phthalonitriles have been synthesised and characterised, which included a novel periodic acid method for forming 4,5-diiodophthalonitrile. Phthalonitrile derivatives with functionalities were synthesised from halogenated phthalonitriles via palladium cross coupling reactions. A novel fumaronitrile anchoring group was synthesised from commercially available methyl 4-(cyanomethyl)-benzoate along with the literature compound 4,5-bis(4-methoxycarbonylphenyl) phthalonitrile. Negishi coupling of 1,1'-dibromo- and ethynylerrocene compounds to halogenated phthalonitriles are also described and characterised along with the synthesis of the solubilising group nonoxyphthalonitrile. The effectiveness of the subphthalocyanine and statistical cyclotetramisation routes to phthalocyanine synthesis using the substituted phthalonitiles has been investigated in the preparation of substituted azapoiphyrines and unsymmetrical phthalocyanines. The dyes contained different donor (r-butyl and nonoxy) and acceptor (carboxylic acid) functional groups, especially designed for sensitisation in DSSC devices. Ring expansion reaction of the subphthalocyanines was very dependent on the substituent and reaction conditions and, in many cases, was not a selective process. Statistical cyclotetramisation of mixed substituted phthalonitriles formed pseudo statistical mixtures where it proved hard to separate the individual compounds from each other. Both the substituted azaporphyrines and unsymmetrical phthalocyanine dyes were used to sensitise naonparticular titiania and constructed into DSSC devices, in which IV and IPCE curves have been measured for each dye. DSSC photoactivity was observed for each unsymmetrical substituted dye. This thesis also describes the synthesis and characterisation of magnesium-aluminium layered double hydroxide clays which, in turn, were used in the preparation of phthalocyanine-suppoited and phthalocyanine-intercalated layered double hydroxides. These substituted clays were then used for the preparation of stabilised pigment systems and were incorporated into model paint formulations based on a PVC matrix. Degradation studies were earned out using the CO2 Flat Panel Reactor using UV irradiated panels coated with the paint formulations. The effect of clay particle morphology, clay particle size, clay-pigment preparation method and pigment loading concentration were all investigated with results showing that > 5 % pigment loading was required to reduce PVC degradation rates. Reflectance measurements were also used to monitor degradation of the panels.
published_date 2010-12-31T03:53:16Z
_version_ 1763752643120857088
score 11.014067

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