A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation

Wu, Lei; Eberhart, Michael; Nayak, Animesh; Brennaman, M. Kyle; Shan, Bing; Meyer, Thomas J.

doi:10.1021/jacs.8b10132

Title: A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation

Journal Article · Tue Oct 16 00:00:00 EDT 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b10132· OSTI ID:1566591

Wu, Lei ^[1]; Eberhart, Michael ^[1]; Nayak, Animesh ^[1]; Brennaman, M. Kyle ^[1]; Shan, Bing ^[1];

^[1]

Univ. of North Carolina at Chapel Hill, Chapel Hill, NC (United States)

Photoanodes in dye-sensitized photoelectrosynthesis cells integrate molecular chromophore/catalyst assemblies on mesoporous n-type metal oxide electrodes for light-driven water oxidation. One limitation for sustainable photoanodes is the stability of chromophore/catalyst assembly on electrode surfaces for long periods. Progress has been made in stabilizing chromophores based on atomic layer deposition, polymer dip coating, C–C cross-coupling by electropolymerization, and silane surface binding, but little progress has been made on catalyst stabilization. We report here the silane-derivatized catalyst, Ru(bda)(L)₂ (bda = 2,2'-bipyridine-6,6'-dicarboxylate, L = 4-(6-(triethoxysilyl)hexyl)pyridine), catalyst 1, which is stabilized on metal oxide electrode surfaces over an extended pH range. A surface stabilization study shows that it maintains its reactivity on the electrode surface toward electrochemical oxidation over a wide range of conditions. Its electrochemical stability on electrode surfaces has been systematically evaluated, and its role as a catalyst for water oxidation has been explored. On surfaces of mesoporous nanostructured core/shell SnO₂/TiO₂, with a TiO₂ stabilized inner layer of the Ru(II) polypyridyl chromophore, [Ru(4,4'-(PO₃H₂)₂bpy)(bpy)₂]²⁺ (RuP²⁺; bpy = 2,2'-bipyridine), highly efficient photoelectrochemical water oxidation catalysis occurs to produce O₂ with a maximum efficiency of ~1.25 mA/cm². Furthermore, long-term loss of catalytic activity occurs with time owing to catalyst loss from the electrode surface by axial ligand dissociation in the high oxidation states of the catalyst.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Alliance for Molecular PhotoElectrode Design for Solar Fuels (AMPED); University of North Carolina, Chapel Hill, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001011

OSTI ID:: 1566591

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 44; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 24 works

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Fighting Deactivation: Classical and Emerging Strategies for Efficient Stabilization of Molecular Electrocatalysts Bairagya, Monojit Das; Bujol, Ryan J.; Elgrishi, Noémie Chemistry – A European Journal https://doi.org/10.1002/chem.201904499	journal	January 2020
Early photophysical events of a ruthenium( ii ) molecular dyad capable of performing photochemical water oxidation and of its model compounds Nastasi, Francesco; Santoro, Antonio; Serroni, Scolastica Photochemical & Photobiological Sciences, Vol. 18, Issue 9 https://doi.org/10.1039/c8pp00530c	journal	January 2019
Recent Advances in the Development of Molecular Catalyst‐Based Anodes for Water Oxidation toward Artificial Photosynthesis Zahran, Zaki N.; Tsubonouchi, Yuta; Mohamed, Eman A. ChemSusChem, Vol. 12, Issue 9 https://doi.org/10.1002/cssc.201802795	journal	November 2018

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Title: A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation

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