Diazonium-Based Covalent Molecular Wiring of Single-LayerGraphene Leads to Enhanced Unidirectional PhotocurrentGeneration through the p-doping Effect

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dc.authoridPalys, Barbara/0000-0003-1113-2546
dc.authoridKargul, Joanna/0000-0003-1410-1905
dc.authoridNawrocka, Ewa Klaudia/0000-0002-4801-7894
dc.authoridKalek, Marcin/0000-0002-1595-9818
dc.authoridRajkiewicz, Adam Ado/0000-0002-9550-6287
dc.authoridMichalowski, Pawel/0000-0002-3299-4092
dc.authoridJacquet, Margot/0000-0002-5842-9761
dc.contributor.authorJacquet, Margot
dc.contributor.authorOsella, Silvio
dc.contributor.authorHarputlu, Ersan
dc.contributor.authorPalys, Barbara
dc.contributor.authorKaczmarek, Monika
dc.contributor.authorNawrocka, Ewa K.
dc.contributor.authorRajkiewicz, Adam A.
dc.date.accessioned2025-03-17T12:25:55Z
dc.date.available2025-03-17T12:25:55Z
dc.date.issued2022
dc.departmentTarsus Üniversitesi
dc.description.abstractDevelopment of robust and cost-effective smart materials requiresrational chemical nanoengineering to provide viable technological solutions for awide range of applications. Recently, a powerful approach based on theelectrografting of diazonium salts has attracted a great deal of attention due to itsnumerous technological advantages. Several studies on graphene-based materialsreveal that the covalent attachment of aryl groups via the above approach could leadto additional beneficial properties of this versatile material. Here, we developed thecovalently linked metalorganic wires on two transparent, cheap, and conductivematerials:fluorine-doped tin oxide (FTO) and FTO/single-layer graphene (FTO/SLG). The wires are terminated with nitrilotriacetic acid metal complexes, whichare universal molecular anchors to immobilize His6-tagged proteins, such asbiophotocatalysts and other types of redox-active proteins of great interest inbiotechnology, optoelectronics, and artificial photosynthesis. We show for thefirsttime that the covalent grafting of a diazonium salt precursor on two differentelectron-rich surfaces leads to the formation of the molecular wires that promote p-doping of SLG concomitantly with a significantlyenhanced unidirectional cathodic photocurrent up to 1 mu Acm-2. Density functional theory modeling reveals that the exceptionallyhigh photocurrent values are due to two distinct mechanisms of electron transfer originating from different orbitals/bands of thediazonium-derived wires depending on the nature of the chelating metal redox center. Importantly, the novel metalorganic interfacesreported here exhibit minimized back electron transfer, which is essential for the maximization of solar conversion efficiency.
dc.description.sponsorshipPolish National Science Centre (OPUS14) [UMO-2018/31/D/ST4/01475]; Polish National Science Centre (SONATA14) [UMO-2018/31/D/ST4/01475]
dc.description.sponsorshipM.J. and J.K. acknowledge the financial support from the Polish National Science Centre (OPUS14 grant no. UMO2017/27/B/ST5/00472 to J.K.). S.O. acknowledges the financial support from the Polish National Science Centre (SONATA14 grant no. UMO-2018/31/D/ST4/01475). Computational resources were provided by the Interdisciplinary Centre for Mathematical and Computational Modeling (ICM, University of Warsaw) under the G83-28 computational grant. We are grateful to Prof. Rafal Jurczakowski (CNBCh UW & Faculty of Chemistry, University of Warsaw, Poland) for his insightful comments on the article and Mateusz Kasztelan (CNBCh UW and Faculty of Chemistry, University of Warsaw, Poland) for his assistance with the Raman spectroscopy measurements.
dc.identifier.doi10.1021/acs.chemmater.2c00088
dc.identifier.endpage3758
dc.identifier.issn0897-4756
dc.identifier.issn1520-5002
dc.identifier.issue8
dc.identifier.scopus2-s2.0-85129001084
dc.identifier.scopusqualityQ1
dc.identifier.startpage3744
dc.identifier.urihttps://doi.org/10.1021/acs.chemmater.2c00088
dc.identifier.urihttps://hdl.handle.net/20.500.13099/1925
dc.identifier.volume34
dc.identifier.wosWOS:000795962300015
dc.identifier.wosqualityQ1
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.language.isoen
dc.publisherAmer Chemical Soc
dc.relation.ispartofChemistry of Materials
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/openAccess
dc.snmzKA_WOS_20250316
dc.subjectSelf-Assembled Monolayers
dc.subjectIndium Tin Oxide
dc.subjectElectron-Transfer Kinetics
dc.subjectElectrochemical Reduction
dc.subjectCarbon Surfaces
dc.subjectOrganic Layers
dc.subjectCharge-Transfer
dc.subjectPhotosystem-I
dc.subjectWork Function
dc.subjectMetal-Oxides
dc.titleDiazonium-Based Covalent Molecular Wiring of Single-LayerGraphene Leads to Enhanced Unidirectional PhotocurrentGeneration through the p-doping Effect
dc.typeArticle

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