Heterogeneous Gold Nanoparticle-Based Catalysts for the Synthesis of Click-Derived Triazoles via the Azide-Alkyne Cycloaddition Reaction

A supported gold nanoparticle-catalyzed strategy has been utilized to promote a click chemistry reaction for the synthesis of 1,2,3-triazoles via the azide-alkyne cycloaddition (AAC) reaction. While the advent of effective non-copper catalysts (i.e., Ru, Ag, Ir) has demonstrated the catalysis of the AAC reaction, additional robust catalytic systems complementary to the copper catalyzed AAC remain in high demand. Herein, Au nanoparticles supported on Al2O3, Fe2O3, TiO2 and ZnO, along with gold reference catalysts (gold on carbon and gold on titania supplied by the World Gold Council) were used as catalysts for the AAC reaction. The supported Au nanoparticles with metal loadings of 0.7–1.6% (w/w relative to support) were able to selectively obtain 1,4-disubstituted-1,2,3-triazoles in moderate yields up to 79% after 15 min, under microwave irradiation at 150 °C using a 0.5–1.0 mol% catalyst loading through a one-pot three-component (terminal alkyne, organohalide and sodium azide) procedure according to the “click” rules. Among the supported Au catalysts, Au/TiO2 gave the best results.

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

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.

Versatility of Supported Gold Nanoparticles on Hydrotalcites used for Oxidation and Reduction Reactions

Regardless of their size, supported gold nanoparticles are largely used for liquid-phase oxidation reactions. Small gold nanoparticles exhibit good performance during the reduction of organic compounds. The direct reduction of carboxylic acid to aldehyde is a famous and familiar reaction in the field of organic chemistry and is considered as one of the fundamental chemical transformations. Herein, we present Au/hydrotalcite, Au/MgO, and Au/Al2O3 systems as heterogeneous versatile catalysts to realize the oxidation of furfural (FF) to furoic acid (FA) and realize the reduction of FA to FF. Experiments showed that in standard aqueous conditions under air, FF can be easily oxidized to FA. When DMSO was used as a solvent to conduct the experiments under an atmosphere of CO2, FA was reduced to FF. The Au/HT series of catalysts was found to be active in both transformations, pointing out the versatility of the gold-based catalysts. The activity significantly depends on the acid-base properties of the catalyst.

Zn Promoted Mg-Al Mixed Oxides-Supported Gold Nanoclusters for Direct Oxidative Esterification of Aldehyde to Ester

The synthesis of ester compounds is one of the most important chemical processes. In this work, Zn-Mg-Al mixed oxides with different Zn2+/Mg2+ molar ratios were prepared via co-precipitation method and supported gold nanoclusters to study the direct oxidative esterification of aldehyde and alcohol in the presence of molecular oxygen. Various characterization techniques such as N2-physical adsorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and CO2 temperature programmed desorption (TPD) were utilized to analyze the structural and electronic properties. Based on the results, the presence of small amounts of Zn2+ ions (~5 wt.%) provoked a remarkable modification of the binary Mg-Al system, which enhanced the interaction between gold with the support and reduced the particle size of gold. For oxidative esterification reaction, the Au25/Zn0.05MgAl-400 catalyst showed the best performance, with the highest turnover frequency (TOF) of 1933 h−1. The active center was believed to be located at the interface between metallic gold with the support, where basic sites contribute a lot to transformation of the substrate.