Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation

Wu, Lei; Nayak, Animesh; Shao, Jing; Meyer, Thomas J.

doi:10.1073/pnas.1902455116

Title: Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation

Journal Article · Thu May 16 00:00:00 EDT 2019 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1902455116· OSTI ID:1610481

Wu, Lei ^[1]; Nayak, Animesh ^[2]; Shao, Jing ^[1];

^[2]

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

Significant progress has been made in designing single-site molecular Ru(II)-polypyridyl-aqua catalysts for homogenous catalytic water oxidation. Surface binding and transfer of the catalytic reactivity onto conductive substrates provides a basis for heterogeneous applications in electrolytic cells and dye-sensitized photoelectrosynthesis cells (DSPECs). Earlier efforts have focused on phosphonic acid (-PO₃H₂) or carboxylic acid (-CO₂H) bindings on oxide surfaces. However, issues remain with limited surface stabilities, especially in aqueous solutions at higher pH under conditions that favor water oxidation by reducing the thermodynamic barrier and accelerating the catalytic rate using atom-proton transfer (APT) pathways. Here, we address the problem by combining silane surface functionalization and surface reductive electropolymerization on mesoporous, nanofilms of indium tin oxide (ITO) on fluorine-doped tin oxide (FTO) substrates (FTO|nanoITO). FTO|nanoITO electrodes were functionalized with vinyltrimethoxysilane (VTMS) to introduce vinyl groups on the electrode surfaces by silane attachment, followed by surface electropolymerization of the vinyl-derivatized complex, [Ru^II(Mebimpy)(dvbpy)(OH₂)]²⁺(1²⁺; Mebimpy: 2,6-bis(1-methyl-1H-benzo[d]imidazol-2-yl)pyridine; dvbpy: 5,5'-divinyl-2,2'-bipyridine), in a mechanism dominated by a grafting-through method. The surface coverage of catalyst 1²⁺ was controlled by the number of electropolymerization cycles. The combined silane attachment/cross-linked polymer network stabilized 1²⁺on the electrode surface under a variety of conditions especially at pH > ~6. Surface-grafted poly1²⁺ was stable toward redox cycling at pH ~ 7.5 over an ~4-h period. Finally, sustained heterogeneous electrocatalytic water oxidation by the electrode gave steady-state currents for at least ~6 h with a Faradaic efficiency of ~68% for O₂ production.

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Research Organization:: University of North Carolina, Chapel Hill, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: SC0001011; SC0015739; 51702221

OSTI ID:: 1610481

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 116, Issue 23; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrocatalytic water oxidation
homogenous and heterogenous
silane surface
functionalization
surface electropolymerization
grafting-through

Title: Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation

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