Supported Gold Catalysts for Base-Free Furfural Oxidation: The State of the Art and Machine-Learning-Enabled Optimization.

Supported gold nanoparticles have proven to be highly effective catalysts for the base-free oxidation of furfural, a compound derived from biomass. Their small size enables a high surface-area-to-volume ratio, providing abundant active sites for the reaction to take place. These gold nanoparticles serve as catalysts by providing surfaces for furfural molecules to adsorb onto and facilitating electron transfer between the substrate and the oxidizing agent. The role of the support in this reaction has been widely studied, and gold-support interactions have been found to be beneficial. However, the exact mechanism of furfural oxidation under base-free conditions remains an active area of research and is not yet fully understood. In this review, we delve into the essential factors that influence the selectivity of furfural oxidation. We present an optimization process that highlights the significant role of machine learning in identifying the best catalyst for this reaction. The principal objective of this study is to provide a comprehensive review of research conducted over the past five years concerning the catalytic oxidation of furfural under base-free conditions. By conducting tree decision making on experimental data from recent articles, a total of 93 gold-based catalysts are compared. The relative variable importance chart analysis reveals that the support preparation method and the pH of the solution are the most crucial factors determining the yield of furoic acid in this oxidation process.

Performance of Cu/ZnO Nanosheets on Electrospun Al2O3 Nanofibers in CO2 Catalytic Hydrogenation to Methanol and Dimethyl Ether.

The synthesis of methanol and dimethyl ether (DME) from carbon dioxide (CO2) and green hydrogen (H2) offers a sustainable pathway to convert CO2 emissions into value-added products. This heterogeneous catalytic reaction often uses copper (Cu) catalysts due to their low cost compared with their noble metal analogs. Nevertheless, improving the activity and selectivity of these Cu catalysts for these products is highly desirable. In the present study, a new architecture of Cu- and Cu/Zn-based catalysts supported on electrospun alumina nanofibers were synthesized. The catalysts were tested under various reaction conditions using high-throughput equipment to highlight the role of the hierarchical fibrous structure on the reaction activity and selectivity. The Cu or Cu/ZnO formed a unique structure of nanosheets, covering the alumina fiber surface. This exceptional morphology provides a large surface area, up to ~300 m2/g, accessible for reaction. Maximal production of methanol (~1106 gmethanolKgCu-1∙h-1) and DME (760 gDMEKgCu-1∙h-1) were obtained for catalysts containing 7% wt. Cu/Zn with a weight ratio of 2.3 Zn to Cu (at 300 °C, 50 bar). The promising results in CO2 hydrogenation to methanol and DME obtained here point out the significant advantage of nanofiber-based catalysts in heterogeneous catalysis.

Ruthenium-Catalyzed Coupling Reactions of CO2 with C2 H4 and Hydrosilanes towards Silyl Esters.

A series of in situ-prepared catalytic systems incorporating RuII precursors and bidentate phosphine ligands has been probed in the reductive carboxylation of ethylene in the presence of triethylsilane as reductant. The catalytic production of propionate and acrylate silyl esters was evidenced by high-throughput screening (HTS) and implemented in batch reactor techniques. The most promising catalyst systems identified were made of Ru(H)(Cl)(CO)(PPh3 )3 and 1,4-bis(dicyclohexylphosphino)butane (DCPB) or 1,1'-ferrocene-diyl-bis(cyclohexylphosphine) (DCPF). A marked influence of water on the acrylate/propionate selectivity was noted. Turnover numbers [mol mol(Ru)-1 ] up to 16 for acrylate and up to 68 for propionate were reached under relatively mild conditions (20 bar, 100 °C, 0.5 mol % Ru, 40 mol % H2 O vs. HSiEt3 ). Possible mechanisms are discussed.

Plasmon-Driven Electrochemical Methanol Oxidation on Gold Nanohole Electrodes.

Direct methanol oxidation is expected to play a central role in low-polluting future power sources. However, the sluggish and complex electro-oxidation of methanol is one of the limiting factors for any practical application. To solve this issue, the use of plasmonic is considered as a promising way to accelerate the methanol oxidation reaction. In this study, we report on a novel approach for achieving enhanced methanol oxidation currents. Perforated gold thin film anodes were decorated with Pt/Ru via electrochemical deposition and investigated for their ability for plasmon-enhanced electrocatalytic methanol oxidation in alkaline media. The novel methanol oxidation anode (AuNHs/PtRu), combining the strong light absorption properties of a gold nanoholes array-based electrode (AuNHs) with surface-anchored bimetallic Pt/Ru nanostructures, known for their high activity toward methanol oxidation, proved to be highly efficient in converting methanol via the hot holes generated in the plasmonic electrode. Without light illumination, AuNHs/PtRu displayed a maximal current density of 13.7 mA/cm2 at -0.11 V vs Ag/AgCl. Enhancement to 17.2 mA/cm2 was achieved under 980 nm laser light illumination at a power density of 2 W/cm2. The thermal effect was negligible in this system, underlining a dominant plasmon process. Fast generation and injection of charge carriers were also evidenced by the abrupt change in the current density upon laser irradiation. The good stability of the interface over several cycles makes this system interesting for methanol electro-oxidation.