Title: Elucidating the Stability and Reactivity of Surface Intermediates on Single-Atom Alloy Catalysts

Journal Article · · ACS Catalysis
 [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Thomas Young Centre and Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London WC1E 7JE, United Kingdom
  2. Department of Chemistry, Tufts University, 62 Talbot Ave., Medford, Massachusetts 02155, United States
  3. Thomas Young Centre, London Centre for Nanotechnology and Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom
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Doping isolated single atoms of a platinum-group metal into the surface of a noble-metal host is sufficient to dramatically improve the activity of the unreactive host yet also facilitates the retention of the host’s high reaction selectivity in numerous catalytic reactions. The atomically dispersed highly active sites in these single-atom alloy (SAA) materials are capable of performing facile bond activations allowing for the uptake of species onto the surface and the subsequent spillover of adspecies onto the noble host material, where selective catalysis can be performed. For example, SAAs have been shown to activate C–H bonds at low temperatures without coke formation, as well as selectively hydrogenate unsaturated hydrocarbons with excellent activity. However, to date, only a small subset of SAAs has been synthesized experimentally and it is unclear which metallic combinations may best catalyze which chemical reactions. To shed light on this issue, we have performed a widespread screening study using density functional theory to elucidate the fundamental adsorptive and catalytic properties of 12 SAAs (Ni-, Pd-, Pt-, and Rh-doped Cu(111), Ag(111), and Au(111)). We considered the interaction of these SAAs with a variety of adsorbates often found in catalysis and computed reaction mechanisms for the activation of several catalytically relevant species (H2, CH4, NH3, CH3OH, and CO2) by SAAs. Finally, we discuss the applicability of thermochemical linear scaling and the Brønsted–Evans–Polanyi relationship to SAA systems, demonstrating that SAAs combine weak binding with low activation energies to give enhanced catalytic behavior over their monometallic counterparts. This work will ultimately facilitate the discovery and development of SAAs, serving as a guide to experimentalists and theoreticians alike.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Organization:
European Union (EU); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-00OR22725; SC0004738; SC0012573
OSTI ID:
1470435
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 6 Vol. 8; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis journal July 2019
Atomic‐Local Environments of Single‐Atom Catalysts: Synthesis, Electronic Structure, and Activity journal October 2019
Single atom alloy catalyst for SO 3 decomposition: enhancement of platinum catalyst's performance by Ag atom embedding journal January 2018
A nickel–iridium alloy as an efficient heterogeneous catalyst for hydrogenation of olefins journal January 2019
Efficient and selective carbon–carbon coupling on coke-resistant PdAu single-atom alloys journal January 2019
Selectivity for ethanol partial oxidation: the unique chemistry of single-atom alloy catalysts on Au, Ag, and Cu(111) journal January 2019
A sacrificial Zn strategy enables anchoring of metal single atoms on the exposed surface of holey 2D molybdenum carbide nanosheets for efficient electrocatalysis journal January 2020
The quantum nature of hydrogen journal January 2019
The quantum nature of hydrogen preprint January 2018

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
42 ENGINEERING
Brønsted−Evans−Polanyi relation
bond activation
catalysis (heterogeneous)
catalyst screening
linear scaling
materials and chemistry by design
mesostructured materials
single-atom alloy
synthesis (novel materials)