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Understanding Oxygen Activation on Nanoporous Gold

Cite this: ACS Catal. 2019, 9, 6, 5204–5216
Publication Date (Web):April 24, 2019
https://doi.org/10.1021/acscatal.9b00682
Copyright © 2019 American Chemical Society
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Abstract

Nanoporous gold (np-Au) is a catalytically highly active material, prepared by selectively dealloying silver from a gold–silver alloy. It can promote aerobic CO oxidation and a range of other oxidation reactions. It has been debated whether the remarkable catalytic properties of np-Au are mainly due to its structural features or whether the residual Ag remaining in the material after dealloying is decisive for the activity, especially for the activation of O2. Recent theoretical studies provided evidence that Ag impurities can facilitate the adsorption and dissociation of O2 on np-Au. However, these studies predicted quite a high activation barrier for O2 dissociation on Au–Ag alloy catalysts, whereas experimentally reported activation energies are much lower. In this work we use the stepped Au(321) surface with Ag impurities, which is arguably a realistic model for np-Au material as well as for Au–Ag catalysts in general. We present alternative routes for O2 activation via its direct reaction with adsorbed CO or H2O. In all of the reactions considered, surface atomic O is generated via a sequence of elementary steps with calculated low activation energies of <0.4 eV with respect to coadsorbed reactants. Ag impurities are shown to increase the adsorption energy of O2 and hence the probability of a surface-mediated reaction versus desorption. We considered four possible mechanisms of CO oxidation in dry and humid environments in a microkinetic modeling study. We show that via the proposed mechanisms water indeed promotes O2 dissociation; nevertheless, the “dry” mechanism, in which CO directly reacts with O2, is by far the fastest route of CO2 formation on pure Au and on Au with Ag impurities. Ag impurities lead to significantly higher turnover rates; thus, calculations point to the key role of Ag in promoting the catalytic activity of Au–Ag alloy systems.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.9b00682.

  • Additional details on the computational methods, discussion of the choice of Ag impurity positions, details on the influence of Ag on the CO* + O2* reaction, discussion of coverage effects for associative CO oxidation, energy diagram for the complete pathway of water-catalyzed O2 activation on Au(321), energy diagrams and optimized structures for the reactions CO* + O* and 2OH* + CO* on Au(321), additional details on the OOH* dissociation, details of microkinetic modeling, Arrhenius plots for mechanisms I–IV and the concentration profile for mechanism II on Ag(321), and Arrhenius plots for mechanism II on AuAg(321)-1Ag and AuAg(321)-2Ag surfaces (PDF)

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This article is cited by 13 publications.

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  2. Ning Rui, Feng Zhang, Kaihang Sun, Zongyuan Liu, Wenqian Xu, Eli Stavitski, Sanjaya D. Senanayake, José A. Rodriguez, Chang-Jun Liu. Hydrogenation of CO2 to Methanol on a Auδ+–In2O3–x Catalyst. ACS Catalysis 2020, 10 (19) , 11307-11317. https://doi.org/10.1021/acscatal.0c02120
  3. Yong Li, Shikun Li, Marcus Bäumer, Elena A. Ivanova-Shor, Lyudmila V. Moskaleva. What Changes on the Inverse Catalyst? Insights from CO Oxidation on Au-Supported Ceria Nanoparticles Using Ab Initio Molecular Dynamics. ACS Catalysis 2020, 10 (5) , 3164-3174. https://doi.org/10.1021/acscatal.9b05175
  4. Yin'an Zhu, Weiji Dai, Xu Zhong, Tao Lu, Ye Pan. In-situ reconstruction of non-noble multi-metal core-shell oxyfluorides for water oxidation. Journal of Colloid and Interface Science 2021, 602 , 55-63. https://doi.org/10.1016/j.jcis.2021.05.170
  5. Ubong J. Etim, Peng Bai, Oz M. Gazit, Ziyi Zhong. Low-Temperature Heterogeneous Oxidation Catalysis and Molecular Oxygen Activation. Catalysis Reviews 2021, 14 , 1-187. https://doi.org/10.1080/01614940.2021.1919044
  6. Yasuhiro Mie, Shizuka Katagai, Chitose Mikami. Electrochemical Molecular Conversion of α-Keto Acid to Amino Acid at a Low Overpotential Using a Nanoporous Gold Catalyst. International Journal of Molecular Sciences 2021, 22 (17) , 9442. https://doi.org/10.3390/ijms22179442
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  8. Jie Wang, Xianmo Gu, Linjuan Pei, Peng Kong, Jin Zhang, Xiaoyu Wang, Ruiyi Wang, Eric R. Waclawik, Zhanfeng Zheng. Strong metal-support interaction induced O2 activation over Au/MNb2O6 (M = Zn2+, Ni2+ and Co2+) for efficient photocatalytic benzyl alcohol oxidative esterification. Applied Catalysis B: Environmental 2021, 283 , 119618. https://doi.org/10.1016/j.apcatb.2020.119618
  9. Jose L. C. Fajín, Ana S. Moura, M. Natália D. S. Cordeiro. First-principles-based kinetic Monte Carlo simulations of CO oxidation on catalytic Au(110) and Ag(110) surfaces. Physical Chemistry Chemical Physics 2021, 106 https://doi.org/10.1039/D1CP00729G
  10. M. Gößler, M. Nachtnebel, H. Schröttner, H. Krenn, E.-M. Steyskal, R. Würschum. Evolution of superparamagnetism in the electrochemical dealloying process. Journal of Applied Physics 2020, 128 (9) , 093904. https://doi.org/10.1063/5.0015397
  11. Yasuhiro Mie, Haruka Takayama, Yu Hirano. Facile control of surface crystallographic orientation of anodized nanoporous gold catalyst and its application for highly efficient hydrogen evolution reaction. Journal of Catalysis 2020, 389 , 476-482. https://doi.org/10.1016/j.jcat.2020.06.023
  12. Ariana Y. Tse, Erin K. Karasz, Karl Sieradzki. Dealloying and morphology evolution of ordered and disordered Cu3Au. Scripta Materialia 2020, 176 , 112-116. https://doi.org/10.1016/j.scriptamat.2019.09.008
  13. Wilke Dononelli, Lyudmila V. Moskaleva, Thorsten Klüner. CO Oxidation over Unsupported Group 11 Metal Catalysts: New Mechanistic Insight from First-Principles. The Journal of Physical Chemistry C 2019, 123 (13) , 7818-7830. https://doi.org/10.1021/acs.jpcc.8b06676