Show simple item record

dc.contributor.advisorMcCulloch, Iain
dc.contributor.authorKosco, Jan
dc.date.accessioned2019-11-28T13:23:05Z
dc.date.available2020-11-08T00:00:00Z
dc.date.issued2019-10
dc.identifier.citationKosco, J. (2019). Organic Semiconductor Nanoparticle Photocatalysts for Hydrogen Evolution from Water. KAUST Research Repository. https://doi.org/10.25781/KAUST-03L3N
dc.identifier.doi10.25781/KAUST-03L3N
dc.identifier.urihttp://hdl.handle.net/10754/660322
dc.description.abstractPhotocatalytic water splitting using solar irradiation has the potential to produce sustainable hydrogen fuel on a large scale. Practical solar energy conversion requires the development of new, stable photocatalysts that operate efficiently under a broad range of visible wavelengths. Organic semiconductors are increasingly being employed as photocatalysts due to their earth abundance, aqueous stability, and optical absorptions that can be tuned to the solar spectrum. However, much remains unknown about the mechanism of organic semiconductor photocatalysis, and significant efficiency improvements need to be made before organic photocatalysts can achieve practical solar energy conversion. In chapter 2 the effect of residual Pd on hydrogen evolution activity in conjugated polymer photocatalysts was systematically investigated using colloidal poly(9,9- dioctylfluorene-alt-benzothiadiazole) (F8BT) nanoparticles (NPs). Residual Pd, originating from the synthesis of F8BT via Pd catalysed polycondensation polymerisation, was observed in the form of homogenously distributed Pd NPs within the polymer. Residual Pd was essential for any hydrogen evolution to be observed from this polymer, and very low Pd concentrations (<40 ppm) were sufficient to have a significant effect on the hydrogen evolution reaction (HER) rate. The HER rate increased linearly with increasing Pd concentration from <1 ppm to approximately 100 ppm, at which point the rate began to saturate. Transient absorption spectroscopy experiments support these conclusions and suggest that residual Pd mediates electron transfer from the F8BT NPs to protons in the aqueous phase. Photocatalysts formed from a single organic semiconductor typically suffer from inefficient intrinsic charge generation, which leads to low photocatalytic activities. In chapter 3 we demonstrate that incorporating a heterojunction between a donor polymer and non-fullerene acceptor in organic NPs can result in hydrogen evolution photocatalysts with greatly enhanced photocatalytic activity. Control of the nanomorphology of these NPs was achieved by varying the stabilizing surfactant employed during NP fabrication, converting it from a core-shell structure to an intermixed donor/acceptor blend, and increasing H2 evolution by an order of magnitude. The resulting photocatalysts display an unprecedentedly high H2 evolution rate of over 60,000 µmolh-1g -1 under 350 to 800 nm illumination and external quantum efficiencies over 6% in the region of maximum solar photon flux.
dc.language.isoen
dc.subjectPhotocatalysis
dc.subjectHydrogen evolution
dc.subjectorganic Photocatalyst
dc.titleOrganic Semiconductor Nanoparticle Photocatalysts for Hydrogen Evolution from Water
dc.typeDissertation
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.rights.embargodate2020-11-08
thesis.degree.grantorKing Abdullah University of Science and Technology
dc.contributor.committeememberLaquai, Frédéric
dc.contributor.committeememberRueping, Magnus
dc.contributor.committeememberDurrant, James R.
thesis.degree.disciplineChemical Science
thesis.degree.nameDoctor of Philosophy
dc.rights.accessrightsAt the time of archiving, the student author of this dissertation opted to temporarily restrict access to it. The full text of this dissertation became available to the public after the expiration of the embargo on 2020-11-08.
refterms.dateFOA2020-11-08T00:00:00Z
kaust.request.doiyes


Files in this item

Thumbnail
Name:
PhD_Thesis_Jan_Kosco_3.pdf
Size:
9.684Mb
Format:
PDF
Description:
Jan Kosco - Final Thesis

This item appears in the following Collection(s)

Show simple item record