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Chasing the Achilles’ Heel in Hybrid Systems of Diruthenium Water Oxidation Catalysts Anchored on Indium Tin Oxide: The Stability of the Anchor

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University of Goettingen, Institute of Inorganic Chemistry, Tammannstraße 4, D-37077 Göttingen, Germany
University of Goettingen, Institute of Materials Physics, Friedrich-Hund-Platz 1, D-37077 Göttingen, Germany
§ University of Goettingen, International Center for Advanced Studies of Energy Conversion (ICASEC), D-37077 Göttingen, Germany
*E-mail for C.J.: [email protected]
*E-mail for F.M.: [email protected]
Cite this: ACS Catal. 2017, 7, 9, 6235–6244
Publication Date (Web):August 1, 2017
https://doi.org/10.1021/acscatal.7b01883
Copyright © 2017 American Chemical Society
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Abstract

The development of hybrid devices for photo-driven water oxidation with dinuclear molecular ruthenium catalysts on solid supports aims both at high efficiencies of the catalyst and at high stability of the linking to the surface. We herein report a systematic study regarding the stability of catalysts anchored on an indium tin oxide (ITO) support via different acid functional groups at the ligand backbone: viz., a single carboxylate anchor, two carboxylate anchors, and a phosphonate anchor. The integrity of the hybrid electrodes ITO|mesoITO|catalyst was evaluated under acidic aqueous conditions as a function of the applied electric potential below and above the onset of the oxygen evolution reaction (OER). Rotating ring disk electrode (RRDE) experiments allowed us to distinguish between the water oxidation and the desorption processes. X-ray photoemission (XPS) and X-ray absorption spectroscopy (XAS) after electrochemical treatment showed high chemical stability of the catalyst core structure but pronounced dependence of the hybrid stability on the oxidation state of the ruthenium center. A combination of these different spectroscopic techniques shed light on the mechanisms underlying catalyst desorption. Specifically, catalysts equipped with carboxylate anchors are found to continuously desorb already at low applied potentials below the OER onset, while for the more rugged phosphonate-based hybrid oxidative P–C(aryl) bond cleavage is proposed to occur, but only after reaching the high-valent RuVRuIV state. These findings reveal specific challenges for anchoring strategies in molecular water oxidation catalysis.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.7b01883.

  • Synthetic procedures, full characterization of compounds, crystallographic details of all structurally characterized compounds, additional electrochemical data, and additional XPS and XAS data (PDF)

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