The use of hexagonal boron nitride (h-BN) as a non-metal heterogeneous catalyst has been a popular subject in research since the discovery of its catalytic properties in 2016. Previous work found that an activation step was necessary for producing an effective catalyst. Density functional theory (DFT) calculations indicate defect sites, such as nitrogen (V N ) and boron (V B ) vacancies, bind favourably to olefins, hydrogen, and oxygen. In particular, the visible fluorescence intensity of processed h-BN increased with the length of exposure to air. The fluorescence behaviour of dh-BN powders when exposed to air after exposure to species such as argon, propene, and carbon dioxide is presented. Density of state calculations for molecular and atomic oxygen bound to V N and V B show that this increase in fluorescence may be due to atomic oxygen binding to V N . The fluorescence emission behaviour observed in dh-BN powders and its relationship to DOS of oxygen species bound to catalytically active defect sites provides a better understanding of potential deactivation modes for catalysts based on dh-BN.

Homogenous single-layer MoS2 films coated with sub-single layer amounts of gold are found to isolate the reaction of methanol with carbon monoxide, the fundamental step toward higher alcohols, from an array of possible surface reactions. Active surfaces were prepared from homogenous single-layer MoS2 films coated with sub-single layer amounts of gold. These gold atoms formed clusters on the MoS2 surface. A gas mixture of carbon monoxide (CO) and methanol (CH3OH) was partially converted to acetaldehyde (CH3CHO) under mild process conditions (308 kPa and 393 K). This carbonylation of methanol to a C2 species is a critical step toward the formation of higher alcohols. Density functional theory modeling of critical steps of the catalytic process identify a viable reaction pathway. Imaging and spectroscopic methods revealed that the single layer of MoS2 facilitated formation of nanoscale gold islands, which appear to sinter through Ostwald ripening. The formation of acetaldehyde by the catalytic carbonylation of methanol over supported gold clusters is an important step toward realizing controlled production of useful molecules from low carbon-count precursors.

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We demonstrate that a fused silica substrate can be rendered active for acetaldehyde (CH3CHO) synthesis from a gas mixture of carbon monoxide (CO) and methanol (CH3OH) under mild process conditions (308 kPa and 393 K) by deposition first of a homogenous single-layer MoS2 film and subsequently of a sub-mnonolayer (1 Angstrom) loading of gold. In operando monitoring of the catalyst performance in a flow reactor reveals uncompromised activity even after 2 hours on stream. The carbonylation of methanol to a C2 species represents a crucial step toward the formation of higher alcohols from syngas derived from methane or biomass. Characterization of the film by imaging and spectroscopy reveals that the single-layer MoS2 film disperses the gold loading into nanoscale islands; density functional theory (DFT) calculations identify low-coordinated edge sites on these islands as active centers for the carbon-carbon coupling at barriers significantly below 1 eV.

Biofuels are an important component of a sustainable fuel future. The implementation of such fuels into existing and new engine designs requires an understanding of their interactions with the engine’s components at temperature. The formation of soot deposits on hot metal components, when in contact with fuels at elevated temperatures, can reduce engine performance. We have devised a test rig to measure soot formation from individual biofuel components. Fuel can be sprayed onto metal surfaces up to 750 °C under a controlled atmosphere. Using this rig, we have studied the formation of carbon deposits on steel, nickel, and aluminum metals using the pure small molecule biofuels and fuel mixture simulants. The amount and chemical identity of the deposits formed were studied using Raman spectroscopy. Using this new method for soot quantification, we can more rapidly screen for low soot forming biofuels as promising biofuel candidates grow.

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