Elucidating the Reactivity of Oxygenates on Single-Atom Alloy Catalysts

Weitian Li; Simran Effricia Madan; Romain Réocreux; Michail Stamatakis

doi:10.1021/acscatal.3c03954

Elucidating the Reactivity of Oxygenates on Single-Atom Alloy Catalysts

ACS Catal. 2023 Nov 27;13(24):15851-15868. doi: 10.1021/acscatal.3c03954. eCollection 2023 Dec 15.

Authors

Weitian Li¹, Simran Effricia Madan¹, Romain Réocreux^{1

2}, Michail Stamatakis¹

Affiliations

¹ Thomas Young Centre and Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London WC1E 7JE, U.K.
² Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K.

Abstract

Doping isolated transition metal atoms into the surface of coinage-metal hosts to form single-atom alloys (SAAs) can significantly improve the catalytic activity and selectivity of their monometallic counterparts. These atomically dispersed dopant metals on the SAA surface act as highly active sites for various bond coupling and activation reactions. In this study, we investigate the catalytic properties of SAAs with different bimetallic combinations [Ni-, Pd-, Pt-, and Rh-doped Cu(111), Ag(111), and Au(111)] for chemistries involving oxygenates relevant to biomass reforming. Density functional theory is employed to calculate and compare the formation energies of species such as methoxy (CH₃O), methanol (CH₃OH), and hydroxymethyl (CH₂OH), thereby understanding the stability of these adsorbates on SAAs. Activation energies and reaction energies of C-O coupling, C-H activation, and O-H activation on these oxygenates are then computed. Analysis of the data in terms of thermochemical linear scaling and Bro̷nsted-Evans-Polanyi relationship shows that some SAAs have the potential to combine weak binding with low activation energies, thereby exhibiting enhanced catalytic behavior over their monometallic counterparts for key elementary steps of oxygenate conversion. This work contributes to the discovery and development of SAA catalysts toward greener technologies, having potential applications in the transition from fossil to renewable fuels and chemicals.