A comparative study on the stability of the furfural molecule on the low index Ni, Pd and Pt surfaces

Abstract

We present a comparative density functional theory investigation of the furfural (Ff) molecule on the low index Ni, Pd and Pt surfaces to understand its geometrical and electronic properties to gain mechanistic insights into the experimentally measured catalytic reactivities of these metal catalysts. We show that the number of metal d- states, which hybridize with the nearest C and O p -orbitals of the Ff molecule, can be used to explain the stability of the Ff molecule on these surfaces. We find that the hybridization between atoms with higher electronegativity and the metal d- states plays a crucial role in determining the stability of these systems. Furthermore, we also find electron transfer from metal to the Ff molecule on the Ni and Pd surfaces, with a reverse process occurring on the Pt surface.

Elucidating the Influence of Metal Surface Composition on Organic Adsorbate Binding Using Active Particle Dynamics

“…Thus, the significantly smaller energy difference potentially suggests that the solvent effect energy correction may instead be metal-dependent. Notably, computational studies have predicted nuanced facet-specific differences in furfural binding: for example, Pt binds furfural more strongly than Pd on (111) facets but less strongly than Pd in some configurations on (110) surfaces . Moreover, other experimental results better corroborate the results in this work with experimental studies in ultra-high vacuum showing desorption of furfural at similar temperatures (365 K) on Pt versus Pd(111) surfaces, , suggesting more comparative binding strengths.…”

“…Notably, computational studies have predicted nuanced facet-specific differences in furfural binding: for example, Pt binds furfural more strongly than Pd on (111) facets but less strongly than Pd in some configurations on (110) surfaces. 17 Moreover, other experimental results better corroborate the results in this work with experimental studies in ultra-high vacuum showing desorption of furfural at similar temperatures (365 K) on Pt versus Pd(111) surfaces, 14,37 suggesting more comparative binding strengths. We note that the rough morphology of the sputtered surface and presence of liquid, while relevant to many catalytic processes, may perturb adsorption processes compared to smooth surfaces in vacuum that complicate direct comparisons.…”

“…Here, we investigate the use of other metal compositions including Pd and Pd-containing alloys. Similar to Pt, Pd catalysts are ubiquitous in industry and are widely used to process and upgrade biomass-derived aromatic oxygenates such as furfural. , Despite their widespread use, trends in furfural binding on Pt versus Pd in vacuum remain unclear ,, and the solvent is expected to further modulate these adsorption strengths; consequently, the relative binding of furfural on Pt and Pd is largely unknown in the liquid phase.…”

Catalysis Hub special collection: editorial

“…The orbital states and hybridization of furfural on a range of metal catalyst-doped surfaces are explored in the article of Chutia and colleagues [ 7 ].…”