Enhancing Photoredox Catalysis in Aqueous Environments: Ruthenium Aqua Complex Derivatization of Graphene Oxide and Graphite Rods for Efficient Visible-Light-Driven Hybrid Catalysts
dc.contributor.author
dc.date.accessioned
2024-03-20T12:07:40Z
dc.date.available
2024-03-20T12:07:40Z
dc.date.issued
2023-12-19
dc.identifier.issn
1944-8244
dc.identifier.uri
dc.description.abstract
A ruthenium aqua photoredox catalyst has been successfully heterogeneneized on graphene oxide (GO@trans-fac-3) and graphite rods (GR@trans-fac-3) for the first time and have proven to be sustainable and easily reusable systems for the photooxidation of alcohols in water, in mild and green conditions. We report here the synthesis and total characterization of two Ru(II)-polypyridyl complexes, the chlorido trans-fac-[RuCl(bpea-pyrene)(bpy)](PF6) (trans-fac-2) and the aqua trans-fac-[Ru(bpea-pyrene)(bpy)OH2](PF6)2 (trans-fac-3), both containing the N-tridentate, 1-[bis(pyridine-2-ylmethyl)amino]methylpyrene (bpea-pyrene), and 2,2′-bipyridine (bpy) ligands. In both complexes, only a single isomer, the trans-fac, has been detected in solution and in the solid state. The aqua complex trans-fac-3 displays bielectronic redox processes in water, assigned to the Ru(IV/II) couple. The trans-fac-3 complex has been heterogenized on different types of supports, (i) on graphene oxide (GO) through π-stacking interactions between the pyrene group of the bpea-pyrene ligand and the GO and (ii) both on glassy carbon electrodes (GC) and on graphite rods (GR) through oxidative electropolymerization of the pyrene group, which yield stable heterogeneous photoredox catalysts. GO@trans-fac-3- and GR/poly trans-fac-3-modified electrodes were fully characterized by spectroscopic and electrochemical methods. Trans-fac-3 and GO@trans-fac-3 photocatalysts (without a photosensitizer) showed good catalytic efficiency in the photooxidation of alcohols in water under mild conditions and using visible light. Both photocatalysts display high selectivity values (>99%) even for primary alcohols in accordance with the presence of two-electron transfer processes (2e–/2H+). GO@trans-fac-3 keeps intact its homogeneous catalytic properties but shows an enhancement in yields. GO@trans-fac-3 can be easily recycled by filtration and reused for up to five runs without any significant loss of catalytic activity. Graphite rods (GR@trans-fac-3) were also evaluated as heterogeneous photoredox catalysts showing high turnover numbers (TON) and selectivity values
dc.description.sponsorship
This research has been financed by AGAUR (Generalitat de Catalunya, projects 2017-SGR-1720, by UdG (Universitat de Girona, PONT2020/05). S.A. and A-M.S. thank the exchange programs ERASMUS+KA107 and ERASMUS+ funded by the European Union.
Open Access funding provided thanks to the CRUE-CSIC agreement with American Chemical Society (ACS)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation.isformatof
Reproducció digital del document publicat a: https://doi.org/10.1021/acsami.3c13156
dc.relation.ispartof
ACS Applied Materials and Interfaces, 2024, vol. 16, núm. 1, p. 507-519
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Attribution 4.0 International
dc.rights.uri
dc.subject
dc.title
Enhancing Photoredox Catalysis in Aqueous Environments: Ruthenium Aqua Complex Derivatization of Graphene Oxide and Graphite Rods for Efficient Visible-Light-Driven Hybrid Catalysts
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
037725
dc.type.peerreviewed
peer-reviewed
dc.identifier.eissn
1944-8252