Theoretical and experimental studies of the adsorption geometry and reaction pathways of furfural over FeNi bimetallic model surfaces and supported catalysts

Abstract

Controlling the activity and selectivity of hydrodeoxygenation (HDO) of biomassderivatives is critical for the utilization of biomass as renewable sources for chemicals and fuels. Furfural, produced by the hydrolysis and dehydration of xylose from hemicellulose, is a promising biomass-derivative to produce important biofuels like 2-methylfuran. Using a combination of density functional theory (DFT) calculations and surface science measurements on Fe/Ni(111) model surfaces, our results indicate that furfural bonds to the bimetallic surfaces primarily through the C=O bond with the furan ring tilted away from the surface, leading to the production of 2-methylfuran through the HDO reaction with furfuryl alcohol being identified as the likely intermediate. Similar preferential interaction of the C=O group over the furan ring is also confirmed on SiO 2-supported FeNi bimetallic catalysts. The similar trends observed on model surfaces and supported catalysts demonstrate the feasibility of using single crystal surfaces to identify precious-metal-free bimetallic catalysts for biomass conversion.

Base metal-Pt alloys: A general route to high selectivity and stability in the production of biofuels from HMF

“…Several studies have argued the high selectivities of the studied bimetallic catalysts is due to the oxophilicity of the secondary metal [9,[12][13][14]. For example, Resasco and coworkers [9] observed that NiFe catalysts showed superior selectivity compared to Ni for the reaction of furfural to methyl furan.…”

Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

“…The mechanism of furfural reaction on hydrogen pre-dosed Fe/Ni(111) surfaces has been published previously [29]. The results of furfural on clean Ni(111) and ML Fe/Ni(111) surfaces are presented here to draw a comparison with C 2 oxygenates, glycolaldehyde and acetaldehyde.…”

“…After deposition, the composition of the ML Fe/Ni(111) surface was estimated using the AES method described previously [28]. The relative Auger intensity ratio (I Fe /I Ni ) for the ML Fe/Ni(111) surface is around 0.15 [29].…”

“…The results of furfural on clean Ni(111) and ML Fe/Ni(111) surfaces are presented here to draw a comparison with C 2 oxygenates, glycolaldehyde and acetaldehyde. As summarized previously [29], there are five possible reaction pathways of furfural on Fe/Ni(111) surfaces: Eq. (8) total decomposition, Eq.…”

Morphology-dependent selective hydrogenation catalysis of hollow AuCu bimetallic nanostructures

“…The application of bimetals in catalytic performance has been attempted by adding a metal to a Ni, Cu, or noble metal base [25][26][27]. In particular, the active site, which plays an important role in the catalytic reaction, has been investigated theoretically and experimentally by controlling the atomic ratio and modifying the surface [28][29][30].…”