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March 15, 2017ACS Energy Letters392 citationsOpen Access

Orientation-Dependent Oxygen Evolution on RuO2 without Lattice Exchange

KSKelsey A. StoerzingerODOscar Díaz‐MoralesMKManuel J. Kolb

Key Points

  • To determine how crystalline surface orientation affects oxygen evolution reaction kinetics on ruthenium dioxide and assess whether lattice oxygen participates in the reaction mechanism.
  • Measured oxygen evolution reaction kinetics on rutile RuO2 (110), (100), (101), and (111) orientations, as well as polyoriented films and particles.
  • Used online electrochemical mass spectrometry in acidic and basic electrolytes to monitor potential lattice oxygen exchange.
  • Conducted density functional theory calculations to evaluate active ruthenium site densities and oxygen binding energies across crystal facets.
  • The rutile (100) facet exhibited the highest oxygen evolution reaction activity among all tested orientations.
  • Online electrochemical mass spectrometry revealed no lattice oxygen exchange during oxygen evolution on oriented facets, polyoriented films, or particles in acidic or basic electrolytes.
  • Density functional theory modeling confirmed that catalytic activity correlates with the density of active ruthenium sites, where higher activity corresponds to weaker oxygen binding.

Abstract

RuO2 catalysts exhibit record activities toward the oxygen evolution reaction (OER), which is crucial to enable efficient and sustainable energy storage. Here we examine the RuO2 OER kinetics on rutile (110), (100), (101), and (111) orientations, finding (100) the most active. We assess the potential involvement of lattice oxygen in the OER mechanism with online electrochemical mass spectrometry, which showed no evidence of oxygen exchange on these oriented facets in acidic or basic electrolytes. Similar results were obtained for polyoriented RuO2 films and particles, in contrast to previous work, suggesting lattice oxygen is not exchanged in catalyzing OER on crystalline RuO2 surfaces. This hypothesis is supported by the correlation of activity with the number of active Ru-sites calculated by density functional theory, where more active facets bind oxygen more weakly. This new understanding of the active sites provides a design strategy to enhance the OER activity of RuO2 nanoparticles by facet engineering.

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Cite This Study

Stoerzinger et al. (2017) studied this question.

synapsesocial.com/papers/6a088888113ba5b476de405ahttps://doi.org/10.1021/acsenergylett.7b00135
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