Mechanistic insights into the structure‐dependent selectivity of catalytic furfural conversion on platinum catalysts

Abstract

The effects of surface structures on the selectivity of catalytic furfural conversion over platinum (Pt) catalysts in the presence of hydrogen have been studied using first principles density functional theory (DFT) calculations and microkinetic modeling. Three Pt model surface structures, that is, flat Pt(111), stepped Pt(211), and Pt 55 cluster are chosen to represent the terrace, step, and corner sites of Pt nanoparticle. DFT results show that the dominant reaction route (hydrogenation or decarbonylation) in furfural conversion depends strongly on the structures (or reactive sites). Using the size-dependent site distribution rule, our microkinetic modeling results indicate the decarbonylation route prevails over smaller Pt particles less than 1.4 nm while the hydrogenation is the dominant reaction route over larger Pt catalyst particles at T 5 473 K and P H 2 5 93 kPa. This is in good agreement with the reported experimental observations.

Reaction Pathways for the Deoxygenation of Biomass‐Pyrolysis‐Derived Bio‐oil on Ru: A DFT Study using Furfural as a Model Compound

“…However, the formation of furan is thermodynamically favored on Pd surfaces, in agreement with experimental observations . Computational studies detailing the mechanism of furfural hydrodeoxygenation to furfuryl alcohol, furan, and MF have also been reported on Pt and Ru surfaces. Cai et al .…”

“…Computational studies detailing the mechanism of furfural hydrodeoxygenation to furfuryl alcohol, furan, and MF have also been reported on Pt and Ru surfaces. Cai et al . calculated activation barriers for furfural hydrogenation on flat Pt(1 1 1), stepped Pt(2 1 1), and Pt 55 clusters and concluded the hydrogenation to furfuryl alcohol to be kinetically favored at terrace and step sites whereas furan formation is favorable at corner sites.…”

Platinum catalysed aerobic selective oxidation of cinnamaldehyde to cinnamic acid

“…Cinnamic acid and styrene production mirrored reactant conversion albeit with a slightly weaker temperature dependence, and indeed exhibit similar apparent activation energies of 24±2 and 27±2 kJ.mol -1 respectively. The latter is in reasonable agreement with DFT calculations for furfural decarbonylation over a Pt55 cluster of 35 kJ.mol -1 [64]. In contrast, 3-phenylpropan-1-ol production was weakly temperature dependent, increasing slightly above 90 °C.…”

Multiscale simulation on thermal stability of supported metal nanocatalysts

“…For example, an Au NP with a diameter of only 5 nm owns around 4,000 atoms, it is enormously too large for first principle‐based DFT calculations. Therefore, it is expected to use different simulation method to solve the problem at the corresponding scale, and sometimes the multiscale simulation strategies are necessary which bridge the models and simulation techniques across a broad range of length and time scales . Based on the study of supported metal nanocatalysts, we mainly introduce here the catalysis application of three widely used simulation methods: the DFT calculation, MD simulation, and ML strategy.…”