Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts

Matheu, Roc; Ertem, Mehmed Z.; Gimbert-Surinach, Carolina; Benet-Buchholz, Jordi; Sala, Xavier; Llobet, Antoni

doi:10.1021/acscatal.7b01860

Title: Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts

Journal Article · Tue Aug 15 00:00:00 EDT 2017 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b01860· OSTI ID:1405933

^[1]; Ertem, Mehmed Z. ^[2]; Gimbert-Surinach, Carolina ^[3]; Benet-Buchholz, Jordi ^[3]; Sala, Xavier ^[4];

^[5]

Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Univ. Rovira i Virgili, Tarragona (Spain)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Barcelona Institute of Science and Technology (BIST), Tarragona (Spain)
Univ. Autonoma de Barcelona, Barcelona (Spain)
Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Univ. Autonoma de Barcelona, Barcelona (Spain)

In this paper, we describe the synthesis, structural characterization, and redox properties of two new Ru complexes containing the dianionic potentially pentadentate [2,2':6',2"-terpyridine]-6,6"-dicarboxylate (tda^2–) ligand that coordinates Ru at the equatorial plane and with additional pyridine or dmso acting as monondentate ligand in the axial positions: [Ru^II(tda-κ-N³O)(py)(dmso)], 1^II and [Ru^III(tda-κ-N³O²)(py)(H₂O)^ax]⁺, 2^III(H₂O)⁺. Complex 1^II has been characterized by single-crystal XRD in the solid state and in solution by NMR spectroscopy. The redox properties of 1^II and 2^III(H₂O)⁺ have been thoroughly investigated by means of cyclic voltammetry and differential pulse voltammetry. Complex 2^II(H₂O) displays poor catalytic activity with regard to the oxidation of water to dioxygen, and its properties have been analyzed on the basis of foot of the wave analysis and catalytic Tafel plots. The activity of 2^II(H₂O) has been compared with related water oxidation catalysts (WOCs) previously described in the literature. Despite its moderate activity, 2^II(H₂O) constitutes the cornerstone that has triggered the rationalization of the different factors that govern overpotentials as well as efficiencies in molecular WOCs. The present work uncovers the interplay between different parameters, namely, coordination number, number of anionic groups bonded to the first-coordination sphere of the metal center, water oxidation catalysis overpotential, pK_a and hydrogen bonding, and the performance of a given WOC. It thus establishes the basic principles for the design of efficient WOCs operating at low overpotentials.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1405933

Report Number(s):: BNL-114431-2017-JA; R&D Project: CO026; KC0304030

Journal Information:: ACS Catalysis, Vol. 7, Issue 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 45 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrocatalysis
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Ru complexes
seven coordination
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Title: Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts

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