X-ray Photoelectron Fingerprints of High-Valence Ruthenium-Oxo Complexes along the Oxidation Reaction Pathway in an Aqueous Environment

Author(s):Show less -

Silva, Jose Luis ^[1] ; Unger, Isaak ^[2] ; Matias, Tiago Araujo ^[3] ; Franco, Leandro Rezende ^[4] ; Damas, Giane ^[1] ; Costa, Luciano T. ^[5] ; Toledo, Kalil C. F. ^[3] ; Rocha, Tulio C. R. ^[6] ; de Brito, Arnaldo Naves ^[7] ; Saak, Clara-Magdalena ^[2] ; Coutinho, Kaline ^[4] ; Araki, Koiti ^[3] ; Bjorneholm, Olle ^[2] ; Brena, Barbara ^[1] ; Araujo, C. Moyses ^[1]

Affiliation

^[1] Uppsala Univ, Dept Phys & Astron, Mat Theory Div, Box S16, S-75120 Uppsala - Sweden

^[2] Uppsala Univ, Dept Phys & Astron, Mol & Condensed Matter Phys Div, Box 516, S-75120 Uppsala - Sweden

^[3] Univ Sao Paulo, Inst Chem, Dept Fundamental Chem, Av Lineu Prestes 748, BR-05508000 Butanta, SP - Brazil

^[4] Univ Sao Paulo, Inst Fis, BR-05508090 Sao Paulo, SP - Brazil

^[5] Univ Fed Fluminense, Dept Fisicoquim, Inst Quim, Outeiro Sao Joao Batista S-N, BR-24020150 Niteroi, RJ - Brazil

^[6] Brazilian Ctr Res Energy & Mat CNPEM, Brazilian Synchrotron Light Lab LNLS, POB 6192, BR-13083970 Campinas, SP - Brazil

^[7] Univ Estadual Campinas, Inst Phys Gleb Wataghin, BR-13083859 Campinas, SP - Brazil

• Document type: Journal article
• Source: Journal of Physical Chemistry Letters; v. 10, n. 24, p. 7636-7643, DEC 19 2019.
• Web of Science Citations: 0

Abstract

Recent advances in operando-synchrotron-based X-ray techniques are making it possible to address fundamental questions related to complex proton-coupled electron transfer reactions, for instance, the electrocatalytic water splitting process. However, it is still a grand challenge to assess the ability of the different techniques to characterize the relevant intermediates, with minimal interference on the reaction mechanism. To this end, we have developed a novel methodology employing X-ray photoelectron spectroscopy (XPS) in connection with the liquid-jet approach to probe the electrochemical properties of a model electrocatalyst, {[}Ru-II(bpy)(2)(py)-(OH2)](2+), in an aqueous environment. There is a unique fingerprint of the extremely important higher-valence ruthenium-oxo species in the XPS spectra along the oxidation reaction pathway. Furthermore, a sequential method combining quantum mechanics and molecular mechanics is used to illuminate the underlying physical chemistry of such systems. This study provides the basis for the future development of in-operando XPS techniques for water oxidation reactions. (AU)

• FAPESP's process: 18/04523-1 - Activation of OER catalysts based on binuclear ruthenium complexes by hydrogen bonding groups
• Grantee: Kalil Cristhian Figueiredo Toledo
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 17/11986-5 - Generation and storage of New Energy: bringing technological development for the country
• Grantee: Ana Flávia Nogueira
• Support Opportunities: Research Grants - Research Centers in Engineering Program
• FAPESP's process: 13/24725-4 - Supramolecular chemistry and nanotechnology
• Grantee: Henrique Eisi Toma
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 17/11631-2 - CINE: computational materials design based on atomistic simulations, meso-scale, multi-physics, and artificial intelligence for energy applications
• Grantee: Juarez Lopes Ferreira da Silva
• Support Opportunities: Research Grants - Research Centers in Engineering Program
• FAPESP's process: 17/50129-0 - Hybrid nanomaterials and nanosystems for solar fuel production
• Grantee: Koiti Araki
• Support Opportunities: Regular Research Grants