Influence of bulky peripheral substituents on subphthalocyanine derivatives: Implications for photocatalytic and photoelectrochemical hydrogen production

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dc.authoridAslan, Emre/0000-0002-7672-2873
dc.authoridAkyildiz, Yigit Osman/0000-0001-7057-7268
dc.authoridDEMIRCIOGLU, Perihan Kubra/0000-0001-9077-5990
dc.authoridKurtay, Gulbin/0000-0003-0920-8409
dc.contributor.authorDogan, Sifa
dc.contributor.authorGuentay, Buket
dc.contributor.authorDemircioglu, Perihan Kuebra
dc.contributor.authorAkyrldrz, Yigit Osman
dc.contributor.authorKoca, Ayse
dc.contributor.authorAslan, Emre
dc.contributor.authorKurtay, Guelbin
dc.date.accessioned2025-03-17T12:27:13Z
dc.date.available2025-03-17T12:27:13Z
dc.date.issued2024
dc.departmentTarsus Üniversitesi
dc.description.abstractA series of novel subphthalocyanine (SubPc) derivatives with bulky electron-donating substituents were synthesized for visible light-induced photocatalytic and photoelectrochemical hydrogen production. SubPc derivatives were decorated with bulky thiophenoxy (coded SubPc 1-2) and phenoxy (coded SubPc 3-4) substituents to compare the influence of the nature of the peripheral bulky substituents on the photophysical and photocatalytic activity of SubPc. The highest photocatalytic performance was obtained from SubPc 4, having diphenyl phenoxy substituents with an H-2 production rate of 7.233 mmol g(-1)h(-1). The photocatalytic hydrogen evolution activities of all SubPc sensitized TiO2 photocatalysts enhanced approximately four times in the presence of Pt co-catalyst. The photocatalysts showed remarkable long-term stability and reproducibility of H-2 evolution over 24-hour irradiation. SubPc 4-based photocatalytic system reached a considerable catalytic activity with the H-2 production of 16.022 mmol g(-1) and a turnover number (TON) value of 34,089 for 24 h irradiation. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) studies were carried out to better understand the photocatalytic abilities of SubPc derivatives and develop a symbiotic connection with experimental investigations. The results highlight the importance of peripheral substituents in modifying electron density, dipole moment, and HOMO-LUMO energy levels and improving SubPc derivative lightharvesting performance. The presence of 2,6-diisopropyl on SubPc derivatives (SubPc 2 and 4) caused a significant change in the properties, resulting in favourable electron transport characteristics and, therefore, improving photocatalytic performance. Furthermore, the incorporation of TiO2, as shown in SubPc 1@TiO2 and SubPc 2@TiO2, resulted in a modest reduction in chemical hardness, implying increased charge transfer inside the molecule and, as a consequence, enhancing its efficacy as a sensitizer. These theoretical discoveries provide a solid foundation for the customized design and optimization of SubPc derivatives for effective photocatalytic applications.
dc.description.sponsorshipScientific and Technological Research Council of Turkey, TUBITAK [121Z232]
dc.description.sponsorshipThis work was supported by The Scientific and Technological Research Council of Turkey, TUBITAK (Grant 121Z232).
dc.identifier.doi10.1016/j.fuel.2023.130356
dc.identifier.issn0016-2361
dc.identifier.issn1873-7153
dc.identifier.scopus2-s2.0-85177569671
dc.identifier.scopusqualityQ1
dc.identifier.urihttps://doi.org/10.1016/j.fuel.2023.130356
dc.identifier.urihttps://hdl.handle.net/20.500.13099/2134
dc.identifier.volume358
dc.identifier.wosWOS:001114420500001
dc.identifier.wosqualityQ1
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.language.isoen
dc.publisherElsevier Sci Ltd
dc.relation.ispartofFuel
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/closedAccess
dc.snmzKA_WOS_20250316
dc.subjectPhotocatalytic hydrogen evolution
dc.subjectGreen hydrogen
dc.subjectArtificial photosynthesis
dc.subjectSubphthalocyanine
dc.subjectDensity Functional Theory
dc.titleInfluence of bulky peripheral substituents on subphthalocyanine derivatives: Implications for photocatalytic and photoelectrochemical hydrogen production
dc.typeArticle

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