Investigating Spillover Energy as a Descriptor for Single-Atom Alloy Catalyst Design

Hannagan, Ryan T.; Lam, Ho Yi; Réocreux, Romain; Wang, Yicheng; Dunbar, Andrew; Lal, Vinita; Çınar, Volkan; Chen, Yunfan; Deshlahra, Prashant; Stamatakis, Michail; Eagan, Nathaniel M.; Sykes, E. Charles H.

doi:10.1021/acs.jpclett.3c02551

Title: Investigating Spillover Energy as a Descriptor for Single-Atom Alloy Catalyst Design

Journal Article · 17 November 2023 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.3c02551 · OSTI ID:2369363

^[1]; Lam, Ho Yi ^[1];

^[2]; Wang, Yicheng ^[1]; Dunbar, Andrew ^[1]; Lal, Vinita ^[1]; Çınar, Volkan ^[1]; Chen, Yunfan ^[1];

^[1];

^[2];

^[1];

^[1]

Tufts Univ., Medford, MA (United States)
Univ. College London (United Kingdom)

The identification of thermodynamic descriptors of catalytic performance is essential for the rational design of heterogeneous catalysts. Here, we investigate how spillover energy, a descriptor quantifying whether intermediates are more stable at the dopant or host metal sites, can be used to design single-atom alloys (SAAs) for formic acid dehydrogenation. Further, using theoretical calculations, we identify NiCu as a SAA with favorable spillover energy and demonstrate that formate intermediates produced after the initial O–H activation are more stable at Ni sites where rate-determining C–H activation occurs. Surface science experiments demonstrated that NiCu(111) SAAs are more reactive than Cu(111) while they still follow the formate reaction pathway. However, reactor studies of silica-supported NiCu SAA nanoparticles showed only a modest improvement over Cu resulting from surface coverage effects. Overall, this study demonstrates the potential of engineering SAAs using spillover energy as a design parameter and highlights the importance of adsorbate–adsorbate interactions under steady-state operation.

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Research Organization:: Tufts Univ., Medford, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0004738

OSTI ID:: 2369363

Journal Information:: Journal of Physical Chemistry Letters, Vol. 14, Issue 47; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
spillover
heterogeneous catalysis
single-atom alloy
DFT
surface science
nanoparticle

Title: Investigating Spillover Energy as a Descriptor for Single-Atom Alloy Catalyst Design

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