Understanding the Role of M/Pt(111) (M = Fe, Co, Ni, Cu) Bimetallic Surfaces for Selective Hydrodeoxygenation of Furfural

Abstract

Selectively cleaving the CO bond of the aldehyde group in furfural is critical for converting this biomass-derived platform chemical to an important biofuel molecule, 2-methylfuran. This work combined density functional theory (DFT) calculations and temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements to investigate the hydrodeoxygenation (HDO) activity of furfural on bimetallic surfaces prepared by modifying Pt(111) with 3d transition metals (Cu, Ni, Fe, and Co). The stronger binding energy of furfural and higher tilted degree of the furan ring on the Co-terminated bimetallic surface resulted in a higher activity for furfural HDO to produce 2-methylfuran in comparison to that on either Pt(111) or Pt-terminated PtCoPt(111). The 3d-terminated bimetallic surfaces with strongly oxophilic 3d metals (Co and Fe) showed higher 2-methylfuran yield in comparison to those surfaces modified with weakly oxophilic 3d metals (Cu and Ni). The effect of oxygen on the HDO selectivity was also investigated on oxygen-modified bimetallic surfaces, revealing that the presence of surface oxygen resulted in a decrease in 2-methylfuran yield. The combined theoretical and experimental results presented here should provide useful guidance for designing Pt-based bimetallic HDO catalysts.

Hierarchically constructed NiO with improved performance for catalytic transfer hydrogenation of biomass-derived aldehydes

“…The multi-functionality of the FF molecule (i.e., C=C, C=O and C-O) can result in several hydrogenation products such as FAOL, tetrahydrofurfuryl alcohol (TFAOL), 2-methylfuran (2-MF) and 2-methyltetrahydrofuran (2-MTHF) [13][14][15]. This renders the selectivity formation of FAOL from FF a remaining challenging as low product yield is often obtained [16,17].…”

Hydro(deoxygenation) Reaction Network of Lignocellulosic Oxygenates

“…Understanding the selective C=O cleavage of FUR is relevant for selective conversion to 2‐MF, in the context of −C=O− catalytic site interactions and oxygen removal for the HDO of long‐carbon‐chain furans and biomass‐derived oxygenates. The stronger binding energy of FUR and higher degree of tilting of the furan ring on the Co‐terminated bimetallic surface result in enhanced HDO activity of FUR to 2‐MF compared with that of either Pt(111) or Pt‐terminated PtCoPt(111) . The 3 d‐terminated bimetallic surfaces with strongly oxophilic 3 d metals (Co and Fe) offer higher 2‐MF yield relative to that of weakly oxophilic 3 d metals (Cu and Ni).…”

“…A combined DFT, TPD, and HREELS study on the HDO activity of FUR on bimetallic surfaces, such as Pt(111), with 3 d oxophilic transition metals (Cu, Ni, Fe, and Co) exhibits higher 2‐MF selectivity than that of weakly oxophilic 3 d metals (Cu, Ni) . Therefore, DFT and experimental results can guide the design of bimetallic surfaces for the HDO of oxygenates for improved selectivity.…”

Exploring the Reaction Mechanisms of Furfural Hydrodeoxygenation on a CuNiCu(111) Bimetallic Catalyst Surface from Computation

“…It was found that, depending on the deposition temperature and reaction condition, the bimetallic surface can possess one of the three following structures: a surface monolayer formed by the occupation of the uppermost surface sites, an underground monolayer formed as a result of the diffusion into the underground area, and intermixed bimetallic surfaces formed as a result of alloying with the surface. 55 In a previous study, Jiang et al 56 developed the PtCoPt(111) bimetallic surface by replacing all the Pt atoms in the second layer of Pt(111) to study the furfural conversion. In our previous study, 33 the most stable Cu(111) surface, with a p (5 × 5)-3L supercell, where the first layer was relaxed and the bottom two layers were fixed, was selected to investigate the selective hydrogenation of furfural to 2-methylfuran.…”

“… 36 In this study, the CuNiCu(111) bimetallic surface was modified by replacing all the Cu atoms in the second layer with Ni atoms; this is in good agreement with the previous investigation. 56 …”