Abstract

Development of robust and cost-effective smart materials requires rational chemical nanoengineering to provide viable technological solutions for a wide range of applications. Recently, a powerful approach based on the electrografting of diazonium salts has attracted a great deal of attention due to its numerous technological advantages. Several studies on graphene-based materials reveal that the covalent attachment of aryl groups via the above approach could lead to additional beneficial properties of this versatile material. Here, we developed the covalently linked metalorganic wires on two transparent, cheap, and conductive materials: fluorine-doped tin oxide (FTO) and FTO/single-layer graphene (FTO/SLG). The wires are terminated with nitrilotriacetic acid metal complexes, which are universal molecular anchors to immobilize His6-tagged proteins, such as biophotocatalysts and other types of redox-active proteins of great interest in biotechnology, optoelectronics, and artificial photosynthesis. We show for the first time that the covalent grafting of a diazonium salt precursor on two different electron-rich surfaces leads to the formation of the molecular wires that promote p-doping of SLG concomitantly with a significantly enhanced unidirectional cathodic photocurrent up to 1 μA cm–2. Density functional theory modeling reveals that the exceptionally high photocurrent values are due to two distinct mechanisms of electron transfer originating from different orbitals/bands of the diazonium-derived wires depending on the nature of the chelating metal redox center. Importantly, the novel metalorganic interfaces reported here exhibit minimized back electron transfer, which is essential for the maximization of solar conversion efficiency.

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