Cullen, Aoibhín ORCID: 0000-0001-8186-3761 (2021) BODIPY copolymers as potential triplet photosensitisers for the photocatalytic generation of hydrogen and enhanced antimicrobial activity. PhD thesis, Dublin City University.
Abstract
Development of efficient and robust organic-based systems for light-driven hydrogen
evolution is crucial to the progression of cost-effective green hydrogen production as
an alternative to the burning of fossil fuels. Conjugated organic polymers offer
potential for advancement in this area mainly fuelled by their tunability, low-cost and
availability of starting materials. The main objective this research was to incorporate
boron-dipyrromethene (BODIPY) chromophores into a polymeric backbone and
investigate the activity of a series of BODIPY polymers for hydrogen generation.
Although extensive research has been carried out on inorganic complexes for
hydrogen evolution, many studies utilise ultraviolet (UV) light to drive these reactions
and their activity using visible light is very poor. This project aims to surmount this
limitation in the development of BODIPY polymers that absorb in the visible region
of the solar spectrum. Furthermore, existing research on inorganic photocatalysts
require the use of expensive and rare metals in their overall synthesis – the polymers
reported in this project are comprised of fully organic-based molecular architectures
and their activity for hydrogen evolution was studied in conjugation with an earthabundant cobalt-based molecular catalyst. The novel BODIPY polymers were
characterised using 1H, 13C NMR spectroscopy, gel permeation chromatography, UVvisible absorption, and photoluminescence spectroscopy. Little is known about the
mechanism of polymeric photocatalysts and their activity that leads to enhancement
in hydrogen evolution. The experimental work presented here provides one of the first
investigations into the photodynamic properties of the polymers in solution-based
studies. This was carried out using both transient absorption (TA) and time-resolved
infrared (TRIR) spectroscopies spanning the early picosecond (ps) to microsecond
(s) timescale, including measurement of a triplet-state lifetime (s timescale), which
is an important photophysical property of the polymer required to advance the
efficiency of the system.
Although this study focuses on the novel BODIPY polymers for hydrogen evolution,
the findings were hypothesised to have bearing on antimicrobial applications as they
possess the desired properties of a successful photodynamic therapy (PDT) agent (i.e.
long-lived triplet lifetime and absorptivity in the visible region of the spectrum).
Hence, the copolymers were also assessed for their ability to generate singlet oxygen
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as a potential for use in antimicrobial applications and were successful both in solution
and when absorbed onto a surface for killing both gram-negative and gram-positive
bacteria.
Inorganic complexes are well established in the field of photocatalytic hydrogen
evolution. Their activity for hydrogen evolution, combined with their superior
photostability make them ideal candidates for viable scale-up options. However, poor
absorptivity in the visible light region of the solar spectrum has limited the application
of inorganic complexes such as ruthenium(II) polypyridyl complexes. A main
objective of the research on novel Ru(II) complexes in this thesis was to extend the
visible light absorptivity of these inorganic complexes through -extended ligands and
addition of ligands with different donor strengths. The investigation of the
photophysics of these complexes is imperative to gain an understanding of the excited
state dynamics and hence optimise these complexes for solar-driven applications.
Metadata
Item Type: | Thesis (PhD) |
---|---|
Date of Award: | November 2021 |
Refereed: | No |
Supervisor(s): | Pryce, Mary |
Subjects: | Physical Sciences > Inorganic chemistry |
DCU Faculties and Centres: | DCU Faculties and Schools > Faculty of Science and Health > School of Chemical Sciences |
Use License: | This item is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 3.0 License. View License |
Funders: | Irish Research Council |
ID Code: | 25981 |
Deposited On: | 01 Nov 2021 13:14 by Mary Pryce . Last Modified 01 Oct 2022 03:30 |
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