Methanol carbonylation to acetaldehyde on Au particles supported by single-layer MoS₂ grown on silica

Abstract

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.

Synthesis of Carbonyl Compounds by Gold-Catalyzed Carbonylation Reactions

“…19 Furthermore, carbonylation of methanol to acetaldehyde over Au clusters on single-layer MoS 2 films was also reported by Blair and co-workers (Scheme 3). 20 A partial of CO and methanol was transformed to acetaldehyde (14) under mild conditions (3.08 MPa and 120 °C). This carbonylation of methanol to a C2 species is a critical step toward the formation of higher alcohols from methanol.…”

Atomic and molecular functionalisation of technological materials: an introduction to nanoscale processes on semiconductor surfaces

“…This behavior is to be contrasted with the strong role played by vacancies in facilitating the chemical reactivity of 2D dichalcogenide MoS 2 [16] and points to the subtleties in the electronic and geometric structure of the trichalcogenides vs the dichalcogenides. Related work by Almeida et al [17] exposes the catalytic activity of a 2D composite catalysts consisting of Au nanoparticles supported on single layer MoS 2 grown on silica towards carbonylation of methanol to acetaldehyde. Accompanying density functional theory modeling provides a mechanistic understanding of this C2 bond formation that is a critical step toward the formation of higher alcohols.…”

“…Related work by Almeida et al [17] exposes the catalytic activity of a 2D composite catalysts consisting of Au nanoparticles supported on single layer MoS 2 grown on silica toward carbonylation of methanol to acetaldehyde. Accompanying DFT modeling provides a mechanistic understanding of this C2 bond formation that is a critical step toward the formation of higher alcohols.…”

Efficient noble metal promoted bimetallic cobalt catalysts in the selective synthesis of acetaldehyde dimethyl acetal

“…Scanning electron microscopy showed that MoS 2 enhanced the formation of Au-rich aggregates on the surface of the catalysts during the synthesis, which played a vital role in the catalytic activity. 12 Peringer et al published in 1996 a more exotic synthesis route to AADMA and other dimethyl acetals starting from a palladium complex. They showed that by using tridentate ligand, as shown in Scheme 1, a general synthesis of dimethylacetals from alkynes can be conducted in the liquid phase.…”

“…Scanning electron microscopy showed that MoS 2 enhanced the formation of Au-rich aggregates on the surface of the catalysts during the synthesis, which played a vital role in the catalytic activity. 12 …”