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Title: Orientation-Dependent Oxygen Evolution on RuO 2 without Lattice Exchange

Abstract

RuO2 catalysts exhibit record activities towards 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 3 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 DFT, 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.

Authors:
ORCiD logo; ; ; ; ; ; ; ; ; ; ORCiD logo; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1364004
Report Number(s):
PNNL-SA-126477
Journal ID: ISSN 2380-8195
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Energy Letters; Journal Volume: 2; Journal Issue: 4
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Stoerzinger, Kelsey A., Diaz-Morales, Oscar, Kolb, Manuel, Rao, Reshma R., Frydendal, Rasmus, Qiao, Liang, Wang, Xiao Renshaw, Halck, Niels Bendtsen, Rossmeisl, Jan, Hansen, Heine A., Vegge, Tejs, Stephens, Ifan E. L., Koper, Marc T. M., and Shao-Horn, Yang. Orientation-Dependent Oxygen Evolution on RuO 2 without Lattice Exchange. United States: N. p., 2017. Web. doi:10.1021/acsenergylett.7b00135.
Stoerzinger, Kelsey A., Diaz-Morales, Oscar, Kolb, Manuel, Rao, Reshma R., Frydendal, Rasmus, Qiao, Liang, Wang, Xiao Renshaw, Halck, Niels Bendtsen, Rossmeisl, Jan, Hansen, Heine A., Vegge, Tejs, Stephens, Ifan E. L., Koper, Marc T. M., & Shao-Horn, Yang. Orientation-Dependent Oxygen Evolution on RuO 2 without Lattice Exchange. United States. doi:10.1021/acsenergylett.7b00135.
Stoerzinger, Kelsey A., Diaz-Morales, Oscar, Kolb, Manuel, Rao, Reshma R., Frydendal, Rasmus, Qiao, Liang, Wang, Xiao Renshaw, Halck, Niels Bendtsen, Rossmeisl, Jan, Hansen, Heine A., Vegge, Tejs, Stephens, Ifan E. L., Koper, Marc T. M., and Shao-Horn, Yang. Wed . "Orientation-Dependent Oxygen Evolution on RuO 2 without Lattice Exchange". United States. doi:10.1021/acsenergylett.7b00135.
@article{osti_1364004,
title = {Orientation-Dependent Oxygen Evolution on RuO 2 without Lattice Exchange},
author = {Stoerzinger, Kelsey A. and Diaz-Morales, Oscar and Kolb, Manuel and Rao, Reshma R. and Frydendal, Rasmus and Qiao, Liang and Wang, Xiao Renshaw and Halck, Niels Bendtsen and Rossmeisl, Jan and Hansen, Heine A. and Vegge, Tejs and Stephens, Ifan E. L. and Koper, Marc T. M. and Shao-Horn, Yang},
abstractNote = {RuO2 catalysts exhibit record activities towards 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 3 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 DFT, 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.},
doi = {10.1021/acsenergylett.7b00135},
journal = {ACS Energy Letters},
number = 4,
volume = 2,
place = {United States},
year = {Wed Mar 15 00:00:00 EDT 2017},
month = {Wed Mar 15 00:00:00 EDT 2017}
}
  • Steady-state polarization curves were recorded to study the kinetics of anodic oxygen evolution at RuO/sub 2/ and TiO/sub 2/-RuO/sub 2/ in acidic and alkaline perchlorate solutions (1 to 8 M in concentration) at 25 and 70/sup 0/C. Reaction orders were determined.
  • Iridium dioxide, IrO 2, is second to the most active RuO 2 catalyst for the oxygen evolution reaction (OER) in acid, and is used in proton exchange membrane water electrolyzers due to its high durability. In order to improve the activity of IrO 2-based catalysts, we prepared RuO 2@IrO 2 core-shell nanocatalysts using carbon-supported Ru as the template. At 1.48 V, the OER specific activity of RuO 2@IrO 2 is threefold that of IrO 2. While the activity volcano plots over wide range of materials have been reported, zooming into the top region to clarify the rate limiting steps ofmore » most active catalysts is important for further activity enhancement. Here, we verified theory-proposed sequential water dissociation pathway in which the O—O bond forms on a single metal site, not via coupling of two adsorbed intermediates, by fitting measured polarization curves using a kinetic equation with the free energies of adsorption and activation as the parameters. Consistent with theoretical calculations, we show that the OER activities of IrO 2 and RuO 2@IrO 2 are limited by the formation of O adsorbed phase, while the OOH formation on the adsorbed O limits the reaction rate on RuO 2.« less
  • Oxygen evolution kinetics was studied at 70 degrees C at RuO/sub 2/ and titaniumruthenium oxide anodes in chlorinated chloride solutions (1 M NaCl, pH 1.4 to 2.25) by recording polarization curves. The reaction orders were determined. The kinetics of anodic oxygen evolution is important for an understanding of electrode behavior and for an estimate of possible current yields of oxygen under the different conditions of electrolysis of NaCl solutions. The results obtained demonstrate that substantial oxygen evolution can occur in chlorinated chloride solutions at active electrodes because of the coupled reaction of chlorine reduction.
  • Colloidal TiO/sub 2/ particles (R/sub h/ = 200 A) when charged with ultrafine deposits of RuO/sub 2/ are extremely active catalysts for water oxidation. A photochemical model system consisting of aqueous Ru(bpy)/sub 3//sup 2 +/ and S/sub 2/O/sub 8//sup 2 -/ solutions is used to probe the mechanistic details of the oxygen evolution reaction 4Ru(bpy)/sub 3//sup 3 +/ + 2H/sub 2/O ..-->.. 4H/sup +/ + O/sub 2/ + 4Ru(bpy)/sub 3//sup 2 +/. Application of combined flash photolysis and conductance techniques shows that hole transfer from Ru(bpy)/sub 3//sup 3 +/ to the catalyst and proton release from water decomposition occur simultaneouslymore » and within milliseconds at 3 mg of RuO/sub 2//L. Mechanistic implications are discussed.« less
  • While the surface atomic structure of RuO 2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO 2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used to determine the surface structural changes on single-crystal RuO2(110) as a function of potential in acidic electrolyte. The redox peaks at 0.7, 1.1 and 1.4 V vs. reversible hydrogen electrode (RHE) could be attributed to surface transitions associated with the successive deprotonation of –H 2O on the coordinatively unsaturated Ru sites (CUS)more » and hydrogen adsorbed to the bridging oxygen sites. At potentials relevant to the oxygen evolution reaction (OER), an –OO species on the Ru CUS sites was detected, which was stabilized by a neighboring –OH group on the Ru CUS or bridge site. Combining potential-dependent surface structures with their energetics from DFT led to a new OER pathway, where the deprotonation of the –OH group used to stabilize –OO was found to be rate-limiting.« less
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