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Title: Surface Orientation Dependent Water Dissociation on Rutile Ruthenium Dioxide

Abstract

Rutile RuO2 is a highly active catalyst for a number of (electro)chemical reactions in aqueous solutions or in humid environments. However, the study of the interaction of RuO2 surfaces with water has been confined largely to the ultrahigh vacuum environment and to the thermodynamically stable (110) surface. In this work, we combine ambient-pressure X-ray photoelectron spectroscopy, in situ surface diffraction, and density functional theory calculations to investigate how four different facets of RuO2 interact with water under humid and electrochemical environments. The vacant coordinatively unsaturated Ru site (CUS) allows for the adsorption and dissociation of water molecules. Different surfaces exhibit unique binding energetics for –H2O and –OH and can allow for different degrees of hydrogen bonding between the adsorbates. Consequently, the degree of water dissociation is found to be sensitive to the surface crystallographic orientation—being maximum for the (101) surface, followed by the (110), (001) and (100) surfaces. In conclusion, this study identifies crystallographic orientation as an important parameter to tune not only the density of active sites but also the energetics for water dissociation; this finding is of great significance for many catalytic reactions, where water is a key reactant, or product.

Authors:
ORCiD logo [1];  [2];  [1];  [3]; ORCiD logo [4];  [5]; ORCiD logo [2]; ORCiD logo [6];  [5]; ORCiD logo [7];  [8]; ORCiD logo [9]; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Technical Univ. of Denmark, Lyngby (Denmark)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States)
  6. Oregon State Univ., Corvallis, OR (United States)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  8. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. di Milano-Bicocca, Milano (Italy)
  9. Technical Univ. of Denmark, Lyngby (Denmark); Imperial College London, London (United Kingdom)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1470909
Alternate Identifier(s):
OSTI ID: 1483418
Grant/Contract Number:  
AC02-76SF00515; 02/MI/MIT/CP/11/07633/GEN/G/00; 12-133817; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 31; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rao, Reshma R., Kolb, Manuel J., Hwang, Jonathan, Pedersen, Anders Filsøe, Mehta, Apurva, You, Hoydoo, Stoerzinger, Kelsey A., Feng, Zhenxing, Zhou, Hua, Bluhm, Hendrik, Giordano, Livia, Stephens, Ifan E. L., and Shao-Horn, Yang. Surface Orientation Dependent Water Dissociation on Rutile Ruthenium Dioxide. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b04284.
Rao, Reshma R., Kolb, Manuel J., Hwang, Jonathan, Pedersen, Anders Filsøe, Mehta, Apurva, You, Hoydoo, Stoerzinger, Kelsey A., Feng, Zhenxing, Zhou, Hua, Bluhm, Hendrik, Giordano, Livia, Stephens, Ifan E. L., & Shao-Horn, Yang. Surface Orientation Dependent Water Dissociation on Rutile Ruthenium Dioxide. United States. https://doi.org/10.1021/acs.jpcc.8b04284
Rao, Reshma R., Kolb, Manuel J., Hwang, Jonathan, Pedersen, Anders Filsøe, Mehta, Apurva, You, Hoydoo, Stoerzinger, Kelsey A., Feng, Zhenxing, Zhou, Hua, Bluhm, Hendrik, Giordano, Livia, Stephens, Ifan E. L., and Shao-Horn, Yang. Thu . "Surface Orientation Dependent Water Dissociation on Rutile Ruthenium Dioxide". United States. https://doi.org/10.1021/acs.jpcc.8b04284. https://www.osti.gov/servlets/purl/1470909.
@article{osti_1470909,
title = {Surface Orientation Dependent Water Dissociation on Rutile Ruthenium Dioxide},
author = {Rao, Reshma R. and Kolb, Manuel J. and Hwang, Jonathan and Pedersen, Anders Filsøe and Mehta, Apurva and You, Hoydoo and Stoerzinger, Kelsey A. and Feng, Zhenxing and Zhou, Hua and Bluhm, Hendrik and Giordano, Livia and Stephens, Ifan E. L. and Shao-Horn, Yang},
abstractNote = {Rutile RuO2 is a highly active catalyst for a number of (electro)chemical reactions in aqueous solutions or in humid environments. However, the study of the interaction of RuO2 surfaces with water has been confined largely to the ultrahigh vacuum environment and to the thermodynamically stable (110) surface. In this work, we combine ambient-pressure X-ray photoelectron spectroscopy, in situ surface diffraction, and density functional theory calculations to investigate how four different facets of RuO2 interact with water under humid and electrochemical environments. The vacant coordinatively unsaturated Ru site (CUS) allows for the adsorption and dissociation of water molecules. Different surfaces exhibit unique binding energetics for –H2O and –OH and can allow for different degrees of hydrogen bonding between the adsorbates. Consequently, the degree of water dissociation is found to be sensitive to the surface crystallographic orientation—being maximum for the (101) surface, followed by the (110), (001) and (100) surfaces. In conclusion, this study identifies crystallographic orientation as an important parameter to tune not only the density of active sites but also the energetics for water dissociation; this finding is of great significance for many catalytic reactions, where water is a key reactant, or product.},
doi = {10.1021/acs.jpcc.8b04284},
journal = {Journal of Physical Chemistry. C},
number = 31,
volume = 122,
place = {United States},
year = {2018},
month = {7}
}

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Figures / Tables:

Figure 1 Figure 1: (A) Water isotherm at room temperature (-25 °C) for the RuO2(110) termination, probing the O ls core level at 735 eV incident energy. Spectra are offset for clarity. Spectra are deconvoluted into gas phase water (H2Ovap) shaded in gray, H2O and $-$OH adsorbed on the CUS site shadedmore » in purple, protonated bridging oxygen in hatched purple, and lattice oxygen outlined in black. (B) Intensity of the protonated species on the CUS, either $-$OH or $-$H2O (filled) and bridge site (open) normalized to the lattice oxygen peak as a function of water pressure at room temperature. ( C) Proposed surface structure at high water pressure showing every second water molecule on the CUS site being dissociated, with the hydrogen donated to the neighboring bridging oxygen ( top view shown in Figure S33).« less

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