TY - JOUR
T1 - Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO2 Electrodes
T2 - Surface Reductive Electropolymerization and Silane Chemistry
AU - Wu, Lei
AU - Kyle Brennaman, M.
AU - Nayak, Animesh
AU - Eberhart, Michael
AU - Miller, Alexander J.M.
AU - Meyer, Thomas J.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/3/27
Y1 - 2019/3/27
N2 - 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.
AB - 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.
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U2 - 10.1021/acscentsci.8b00914
DO - 10.1021/acscentsci.8b00914
M3 - Article
AN - SCOPUS:85063596726
SN - 2374-7943
VL - 5
SP - 506
EP - 514
JO - ACS Central Science
JF - ACS Central Science
IS - 3
ER -