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Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO2 Electrodes: Surface Reductive Electropolymerization and Silane Chemistry.

ABSTRACT: Stabilization is a critical issue in the long term operation of dye-sensitized photoelectrosynthesis cells (DSPECs) for water splitting or CO2 reduction. The cells require a stable binding of the robust molecular chromophores, catalysts, and chromophore/catalyst assemblies on metal oxide semiconductor electrodes under the corresponding (photoelectro)chemical conditions. Here, an efficient stabilization strategy is presented based on functionalization of FTO|nanoTiO2 (mesoporous, nanostructured TiO2 deposited on fluorine-doped tin oxide (FTO) glass) electrodes with a vinylsilane followed by surface reductive electropolymerization of a vinyl-derivatized Ru(II) polypyridyl chromophore. The surface electropolymerization was dominated by a grafting-through mechanism, and rapidly completed within minutes. Chromophore surface coverages were controlled up to three equivalent monolayers by the number of electropolymerization cycles. The silane immobilization and cross-linked polymer network produced highly (photo)stabilized chromophore-grafted FTO|nanoTiO2 electrodes. The electrodes showed significant improvements over structures based on atomic layer deposition and polymer dip-coating stabilization methods in a wide pH range from pH ? 1 to pH ? 12.5 under both dark and light conditions. Under illumination, with hydroquinone added as a sacrificial electron transfer donor, a photoresponse for sustained electron transfer mediation occurred for at least ?20 h in a pH ? 7.5 phosphate buffer (0.1 M NaH2PO4/Na2HPO4, with 0.5 M NaClO4). The overall procedure provides an efficient way to fabricate highly stabilized molecular assemblies on electrode surfaces with potential applications for DSPECs in solar fuels.

SUBMITTER: Wu L

PROVIDER: S-EPMC6439529 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO2 Electrodes: Surface Reductive Electropolymerization and Silane Chemistry.

Wu Lei L Brennaman M Kyle MK Nayak Animesh A Eberhart Michael M Miller Alexander J M AJM Meyer Thomas J TJ

ACS central science 20190215 3

Stabilization is a critical issue in the long term operation of dye-sensitized photoelectrosynthesis cells (DSPECs) for water splitting or CO2 reduction. The cells require a stable binding of the robust molecular chromophores, catalysts, and chromophore/catalyst assemblies on metal oxide semiconductor electrodes under the corresponding (photoelectro)chemical conditions. Here, an efficient stabilization strategy is presented based on functionalization of FTO|nanoTiO2 ...[more]

PMID: 30937378

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Project description:This paper describes an electropolymerization-based on-chip valving system, accomplished by electrosynthesis of conductive polymeric ionic liquid (CPIL) films at selected points within an array of bipolar electrodes (BPEs), in which each of these wireless electrodes spans an IL-aqueous phase boundary. The low viscosity and high hydrophobicity of the CPIL precursor allow it to be patterned by established microfluidic methods. This advancement has the potential to impact microscale analysis because it allows on-demand creation of solid CPIL microstructures at locations specified by microfluidics, phase boundaries, and electrode potentials. To achieve this outcome, an imidazolium-based IL was functionalized with a pyrrole moiety, and the viscosity was tuned by choosing the appropriate counterion to form a CPIL with the desired viscosity, hydrophobicity, and oxidation potential. This monomer species was then introduced into a microfluidic device, which was prefilled with an aqueous buffer solution. The device comprised many parallel microchannels lined with nanoliter-scale chambers. BPEs interconnected the channels such that the BPE tips were each aligned to a chamber opening. The electrodes contacting the outermost channels were connected directly to a power supply and functioned as driving electrodes. The CPIL displaced the buffer in the channels and established a phase boundary at the opening of each chamber, thereby digitizing the aqueous phase. Finally, an alternating square waveform (under mode 1) was applied for 5 min to yield immobilized polymer films at a location defined by the BPE poles. In total, three modes were developed and three corresponding polymer film patterns were formed. Under mode 2, a DC power supply was used to achieve a dissymmetrical polymer film pattern, and, under mode 3, a regional polymer film pattern was formed under an AC potential with a DC offset. Our preliminary results demonstrate that the generated polymer films are immobile and sufficiently thick to seal the chambers at room temperature over the duration of our observation window (50 min), and this seal is maintained even at elevated temperatures that induce partial evaporation of the chamber contents. A key point is that this method is compatible with a preceding step─dielectrophoretic capture of single melanoma cells within the nanoliter-scale chambers.

Dataset Information

Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO2 Electrodes: Surface Reductive Electropolymerization and Silane Chemistry.

Publications

Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO<sub>2</sub> Electrodes: Surface Reductive Electropolymerization and Silane Chemistry.

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