Subnanometric Cu Clusters on Atomically Fe-doped MoO2 for Furfural Upgrading to Aviation Biofuels

Single cluster catalysts (SCCs) are considered as versatile boosters in heterogeneous catalysis due to their modifiable single cluster sites and supports. In this work, we report subnanometric Cu clusters dispersed on Fe-doped MoO2 support for biomass-derived furfural upgrading. Systematical characterizations suggest uniform Cu clusters (composing four Cu atoms in average) are homogeneously immobilized on the atomically Fe-doped ultrafine MoO2 nanocrystals (Cu4/Fe0.3Mo0.7O2@C). The atomic doping of Fe into MoO2 leads to significantly modified electronic structure and consequently charge redistribution inside the supported Cu clusters. The as-prepared Cu4/Fe0.3Mo0.7O2@C shows superior catalytic performance in the oxidative coupling of furfural with C3~C10 primary/secondary alcohols to produce C8~C15 aldehydes/ketones (aviation biofuel intermediates), outperforming the conventionally prepared counterparts. DFT calculations and control experiments are further carried out to interpret the structural and compositional merits of Cu4/Fe0.3Mo0.7O2@C in the oxidative coupling reaction, and elucidate the reaction pathway and related intermediates.

A Comparison Study of Soot Precursor and Aggregate Property Between Algae-Based Aviation Biofuel and Aviation Kerosene RP-3 in Laminar Flame

Algae-based aviation biofuel shows the potential to reduce soot emission in flight. A comparison study of soot precursor and aggregate property between algae-based biofuel and aviation kerosene RP-3 in laminar flame was conducted to investigate the reason of biofuel’s less soot formation. The soot precursors were determined by the fringe lengths of soot particles. At a typical dimensionless height DH = 0.50 of both flames, the geometric mean fringe lengths of biofuel and RP-3 are measured to be 0.67 and 0.73 nm, respectively, approximating to the size of five-ringed (A5) and seven-ringed (A7) poly-aromatic hydrocarbon, respectively. An A5 growth mechanism was then added to biofuel surrogate mechanisms for soot formation simulation. Since the carbon number component of biofuel is wide and difficult for comprehensive mechanism development, two surrogate mechanisms were developed. One is based on the C8–C16 n-alkane that covers biofuel’s main components, and the other one is based on biofuel’s average carbon number to simplify the mechanism. Meanwhile, an A7 growth mechanism was added to a popular RP-3 mechanism. The soot formation simulation with the combination mechanisms for both fuels provides a better agreement with the measured primary particle diameter and suggests that the reason for less soot production by biofuel is its less soot precursor production that weakens soot nucleation and growth. Lastly, the soot fractal dimension of biofuel is smaller than that of RP-3, indicating that biofuel has a looser soot aggregate.