Support Effect of Ru Catalysts for Efficient Conversion of Biomass-Derived 2,5-Hexanedione to Different Products

Abstract

Tuning the activity of supported metals by changing the properties of supports is a highly attractive strategy to realize some important reactions in biomass transformation. Herein, Ru nanoparticles supported on montmorillonite (MMT) and hydroxyapatite (HAP), denoted as Ru/MMT and Ru/HAP, were prepared. It was found that the activity of the Ru catalysts for different routes to convert biomass-derived 2,5-hexanedione (2,5-HD) could be controlled by the support materials. Ru/MMT was active for the synthesis of dimethyltetrahydrofuran from hydrogenation of 2,5-HD at 90 °C, while Ru/HAP showed excellent performance on the conversion of 2,5-HD into N-substituted tetrahydropyrroles at 30 °C via direct reductive amination. Systematic study revealed that the property of support materials influenced the activity of Ru/MMT and Ru/HAP for the different routes, affording different reaction pathways for conversion of 2,5-HD.

Efficient Electrocatalytic Oxidation of 5-Hydroxymethylfurfural Coupled with 4-Nitrophenol Hydrogenation in a Water System

“…Biomass is known as a sustainable and renewable nonfossil carbon resource, and it is the most promising clean energy to replace the existing fossil fuels and organic molecules. − 5-Hydroxymethylfurfural (HMF), one of the biomass-derived platform molecules, has been considered as a versatile precursor for a series of valuable chemicals. − In the process of HMF conversion routes, the oxidation of HMF to 2,5-furandicarboxylic acid (FDCA) has attracted significant attention because FDCA is an important intermediate chemical with immense potential in the field of fine chemicals and medicines. − The traditional method for oxidation of HMF to FDCA not only requires harsh reaction conditions (high temperature and pressure) but also involves the demand for precious metal catalysts. − Recently, the electrocatalysis of HMF exhibited unique advantages such as mild conditions, simple operation, an inexpensive catalyst, and environmental friendliness. − However, the design concepts of most catalysts mainly concentrated on the conversion of HMF, whereas the catalytic active site, the oxidation route, and the catalytic mechanism are not clear, which significantly limited the application prospects of these catalysts in electrocatalytic HMF oxidation. Thus, it is very necessary to design a highly efficient electrocatalyst to selectively oxidize HMF to FDCA and in-depth learn the catalytic mechanism.…”

Iodine‐Modified Pd Catalysts Promote the Bifunctional Catalytic Synthesis of 2,5‐Hexanedione from C6 Furan Aldehydes

“…[17][18][19] Among these compounds, 2,5-hexanedione (HD) is an important high-value commodity chemical for performing various upgrades to solvents, polymers, fragrances, and drugs. [20][21][22][23][24] The hydrogenative ring-opening of 5-methylfurfural (MF) to HD has been widely reported over combinations of metals and acids (such as Au/TiO 2 , Pd/Nb 2 O 5 , Ni 2 P/mordenite, Ni 2 P + HZSM-5) under a water solvent by successive C=O hydrogenation, ring-opening, and C=C hydrogenation. [19,[25][26][27] The reaction suffers a high reaction temperature of 130-250 °C.…”

“…To decrease the carbon footprint and develop a sustainable economy, these catalysts have attracted widespread interest for use in the upgrading of unsaturated biomass‐derived C 6 furfurals (5‐methylfurfural, 5‐hydroxymethylfurfural) to valuable chemicals, such as hydrogenative etherification to furan ethers (2‐alkoxymethyl‐5‐methylfuran, 2,5‐bisalkoxymethylfuran), [5–7] hydrogenative ring‐rearrangement to cyclic ketones (3‐methylcyclopentanone, 3‐hydroxymethylcyclopentanone), [8–13] hydrogenative hydrogenolysis to 2,5‐dimethylfuran and 2,5‐dimethyl tetrahydrofuran, [14–16] hydrogenative ring‐opening to linear ketones (1‐hydroxyl‐2,5‐hexanedione, 2,5‐hexanedione) [17–19] . Among these compounds, 2,5‐hexanedione (HD) is an important high‐value commodity chemical for performing various upgrades to solvents, polymers, fragrances, and drugs [20–24] …”

Impact of Cerium Oxide on the State and Hydrogenation Activity of Ruthenium Species Incorporated on Mesocellular Foam Silica

“…Newman et al [ 6 ] studied the effect of Ru particle size on various supports (mesoporous silica, active carbon and metal oxides) and obtained particle sizes ranging from 1.5 to 256 nm. In another work [ 7 ], some changes in the acid-base properties of the support for Ru particles led to diverse results in the selectivity and conversion of 2,5-hexanedione hydrogenation.…”