On the Operando Structure of Ruthenium Oxides during the Oxygen Evolution Reaction in Acidic Media

Deka, Nipon; Jones, Travis E.; Falling, Lorenz J.; Sandoval-Diaz, Luis-Ernesto; Lunkenbein, Thomas; Velasco-Velez, Juan-Jesus; Chan, Ting-Shan; Chuang, Cheng-Hao; Knop-Gericke, Axel; Mom, Rik V.

doi:10.1021/acscatal.3c01607

Title: On the Operando Structure of Ruthenium Oxides during the Oxygen Evolution Reaction in Acidic Media

Journal Article · 19 May 2023 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.3c01607 · OSTI ID:1998136

^[1];

^[2];

^[3]; Sandoval-Diaz, Luis-Ernesto ^[4]; Lunkenbein, Thomas ^[4];

^[4]; Chan, Ting-Shan ^[5];

^[6]; Knop-Gericke, Axel ^[4];

^[1]

Leiden University (Netherlands)
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Fritz Haber Institute of the Max Planck Society, Berlin (Germany)
National Synchrotron Radiation Research Center (NSRRC), Hsinchu (Taiwan)
Tamkang University, Taipei (Taiwan)

In the search for rational design strategies for oxygen evolution reaction (OER) catalysts, linking the catalyst structure to activity and stability is key. However, highly active catalysts such as IrO_x and RuO_x undergo structural changes under OER conditions, and hence, structure–activity–stability relationships need to take into account the operando structure of the catalyst. Under the highly anodic conditions of the oxygen evolution reaction (OER), electrocatalysts are often converted into an active form. Here, we studied this activation for amorphous and crystalline ruthenium oxide using X-ray absorption spectroscopy (XAS) and electrochemical scanning electron microscopy (EC-SEM). We tracked the evolution of surface oxygen species in ruthenium oxides while in parallel mapping the oxidation state of the Ru atoms to draw a complete picture of the oxidation events that lead to the OER active structure. Our data show that a large fraction of the OH groups in the oxide are deprotonated under OER conditions, leading to a highly oxidized active material. The oxidation is centered not only on the Ru atoms but also on the oxygen lattice. This oxygen lattice activation is particularly strong for amorphous RuO_x. We propose that this property is key for the high activity and low stability observed for amorphous ruthenium oxide.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1998136

Report Number(s):: LA-UR-23-26592

Journal Information:: ACS Catalysis, Vol. 13, Issue 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
operando XAS
ruthenium oxide
oxygen evolution reaction
electrocatalysis
O K-edge XAS
Ru M-edge XAS
Ru L-edge XAS

Title: On the Operando Structure of Ruthenium Oxides during the Oxygen Evolution Reaction in Acidic Media

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