Interface reconstruction strategy enabling the efficient light-driven amination of furfuryl alcohol.

To avoid undesired polymerization and maximize the selectivity of alkyl levulinate from the acid-catalyzed conversion of biomass-derived furfuryl alcohol, the effects of catalyst and reaction parameters on the formations of humin and alkyl levulinate were investigated. The results show that Amberlyst 15, of moderate acidic strength, was more favorable for the selective conversion of furfuryl alcohol to alkyl levulinate, and heteropolyacids of strong acidic strength tended to promote furfuryl alcohol polymerization. Compared with water as a reaction medium, alcohol significantly lowered humin formation and enhanced the yield of the resulting products. The formations of humin and alkyl levulinate were both favored at high catalyst loadings and reaction temperatures. An augmentation in initial furfuryl alcohol concentration caused an increase in humin formation and a decrease in alkyl levulinate yield. A high alkyl levulinate yield of up to 94% (100% furfuryl alcohol conversion) was achieved at 110 °C for 4 h with 5 g/L Amberlyst 15 catalyst and an initial furfuryl alcohol concentration of 0.1 mol/L. At this point, about 5% furfuryl alcohol was polymerized to form the humin, and its polymerization occurred mainly during the initial reaction stage.

To avoid undesired polymerization and maximize the selectivity of alkyl levulinate from the acid-catalyzed conversion of biomass-derived furfuryl alcohol, the effects of catalyst and reaction parameters on the formations of humin and alkyl levulinate were investigated. The results show that Amberlyst 15, of moderate acidic strength, was more favorable for the selective conversion of furfuryl alcohol to alkyl levulinate, and heteropolyacids of strong acidic strength tended to promote furfuryl alcohol polymerization. Compared with water as a reaction medium, alcohol significantly lowered humin formation and enhanced the yield of the resulting products. The formations of humin and alkyl levulinate were both favored at high catalyst loadings and reaction temperatures. An augmentation in initial furfuryl alcohol concentration caused an increase in humin formation and a decrease in alkyl levulinate yield. A high alkyl levulinate yield of up to 94% (100% furfuryl alcohol conversion) was achieved at 110 °C for 4 h with 5 g/L Amberlyst 15 catalyst and an initial furfuryl alcohol concentration of 0.1 mol/L. At this point, about 5% furfuryl alcohol was polymerized to form the humin, and its polymerization occurred mainly during the initial reaction stage.

A Modular Strategy for the Direct Catalytic Asymmetric α-Amination of Carbonyl Compounds

Selective conversion of biomass-derived furfuryl alcohol into n-butyl levulinate over sulfonic acid functionalized TiO2 nanotubes

Bifunctional g-C3N4 nanospheres/CdZnS QDs S-scheme photocatalyst with boosted H2 evolution and furfural synthesis mechanism

The aquasoluble FeIII complexes [Fe(H2 O)3 (L1 )] ⋅ 4H2 O (Fe1) and [Fe(H2 O)3 (L2 )] ⋅ 3H2 O (Fe2), bearing the basic forms of 5-chloro-3-(2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl)-2-hydroxy-benzenesulfonic acid (H3 L1 ) and 3-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)-2-hydroxy-5-nitrobenzenesulfonic acid (H3 L2 ), were incorporated for the first time into amine-functionalized SBA-15 support via an impregnation method. The successful preparation of the composites was confirmed by Fourier-Transform Infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), scanning electron microscope (SEM/EDS), transmission electron microscopy (TEM), elemental analysis, and nitrogen adsorption-desorption isotherms. The resulting Fe1@aptesSBA-15 and Fe2@aptesSBA-15 composites were tested as the first SBA-15-based heterogeneous catalysts for the conversion of furfuryl alcohol under mild reaction conditions (80 to 100 °C) and with an environmentally friendly oxidant (TBHP, 70 % aq. sol. with 1 : 1 oxidant/substrate molar ratio). The influence of various factors, such as reaction time, amounts of oxidant and catalyst, was investigated. The reaction time can be fairly reduced by adopting a microwave-assisted method allowing it to reach complete conversion after 0.25 h, in the absence of any added solvent or additive. Under these conditions, a vigorous furfuryl alcohol polymerization process occurred, with furfural as a by-product. Recycling studies were carried out for Fe2@aptesSBA-15 and after four consecutive runs, the overall conversion of furfuryl alcohol remained high (≥99 %), without an appreciable change in the obtained yield.

The titania nanotubes-bonded sulfamic acid (TNTs-NHSO3H) catalyst was designed and successfully fabricated by the post-synthesis modification method. The as-prepared catalyst was characterized by a variety of characterization techniques, including Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, and thermogravimetry-differential thermal gravimetry (TG-DTG). The crystal structure of the TNTs still maintained during the modification process. Although the BET surface area was decreased, the amount of Brønsted acid sites can be efficiently fabricated on the TNTs. The catalytic activity of TNTs-NHSO3H was examined for the synthesis of n-butyl levulinate (BL) from levulinic acid (LA) and furfuryl alcohol (FA). A relatively high selectivity (99.6%) at 99.3% LA conversion was achieved for esterification of levulinic acid owing to the strong Brønsted acidity sites. And also, the TNTs-NHSO3H catalyst exhibited a higher reactivity for alcoholysis of FA and the yield of BL reached 90.4% with 100% FA conversion was obtained under the mild conditions.

It is of great significance to use biomass-based furfuryl alcohol to produce oxygenated chemicals to replace petroleum-based chemicals. In this paper, a series of bifunctional Cu-MFI catalysts were developed, and the properties of biomass-based furfuryl alcohol to pentanediol, including 1,5-pentanediol and 1,2 pentanediol, were investigated. These catalysts were synthesized by ammonia evaporation method by loading copper nanoparticles on MFI molecular sieve systems with different silicon aluminum ratios. Among them, Cu-MFI (60)-AE catalyst containing abundantly Brønsted acid protons shows excellent performance, achieving 99.7% furfuryl alcohol conversion and 91% pentanediol selectivity under mild reaction conditions. The high catalytic activity can be attributed to the highly dispersed Cu species and Brønsted acid protons. Brønsted acid protons play a decisive role in the highly selective formation of 1,5-PDO. This paper can develop an economical and feasible path for converting furfuryl alcohol into high value-added fine chemicals.

Continuous Flow valorization of furanics: From decarbonylation of 5-Hydroxymethyl-furfural to furfuryl alcohol conversion into valuable oxidative coupling products

The conversion of furfuryl alcohol (FAL) to levulinic acid over AmberlystTM 15 in aqueous media was investigated using a combination of liquid chromatography-mass spectrometry (LC-MS) measurements, isotopic labeling studies, nuclear magnetic resonance (NMR) spectroscopy, and ab initio quantum chemical calculations using the G4MP2 method. The results of these combined studies showed that one of the major reaction pathways takes place via a geminal diol species (4,5,5-trihydroxypentan-2-one, denoted as intermediate A), formed by the addition of two water molecules to FAL, where two of the oxygen atoms from FAL are retained. This geminal diol species can also be produced from another intermediate found to be a dimer-like species, denoted as intermediate B. This dimer-like species is formed at the early stages of reaction, and it can also be converted to intermediate A, indicating that intermediate B is the product of the reaction of FAL with another early intermediate. Quantum chemical calculations suggested this to be a protonated acyclic species. Reaction of this early intermediate with water produces intermediate A, while reaction with FAL produces intermediate B.

BACKGROUNDThe sustainable synthesis of cyclopentanone from biomass‐derived furfural and/or furfuryl alcohol has attracted widespread attention in the carbon‐neutral industry. In this study, we investigated the influence of support textural properties and acidity on the catalytic performance of supported CuNi alloy nanoparticles (5 wt%–5 wt%).RESULTSCuNi alloy particles with a size of approximately 16 nm were obtained on SiO2 and Al‐containing siliceous materials (Al‐MCM‐41, MCM‐22, USY‐6, ZSM‐5 and H‐Beta). The number of total acid sites follows the trend of 5Cu5Ni/H‐Beta (1.37 mmol g−1) > 5Cu5Ni/ZSM‐5 (1.03 mmol g−1) > 5Cu5Ni/MCM‐22 (0.87 mmol g−1) > 5Cu5Ni/USY‐6 (0.70 mmol g−1) > 5Cu5Ni/Al2O3 (0.35 mmol g−1) > 5Cu5Ni/SiO2 (0.24 mmol g−1). 5Cu5Ni/ZSM‐5 shows the largest amount of strong acid sites with ca 0.43 mmol g−1. Catalytic tests indicated that furfuryl alcohol is a more effective starting reagent for this process than furfural. When an aqueous solution of furfuryl alcohol (5 wt%) was used, 5Cu5Ni/H‐Beta exhibited 67% selectivity for cyclopentanone with almost 100% furfuryl alcohol conversion. Moreover, the 5Cu5Ni/H‐Beta catalyst exhibited good reusability.CONCLUSIONSupports with moderately acidic sites and fewer strongly acidic sites (MCM‐41, MCM‐22, USY‐6 and H‐Beta) favored the tandem synthesis of cyclopentanone from furfuryl alcohol. © 2025 Society of Chemical Industry (SCI).

The TiO2 supported Ru-based catalysts were prepared with 1.5 wt% Ru and 0–0.8 wt% Co on various TiO2 (anatase, rutile, P-25, and sol–gel TiO2) and studied in the liquid-phase selective hydrogenation of furfural to furfuryl alcohol (FA) under mild conditions (50 °C and 2 MPa H2). The presence of high anatase crystallographic composition on TiO2 support was favorable for enhancing hydrogenation activity, while the strong interaction between Ru and TiO2 (Ru–TiOx sites) was required for promoting the selectivity to FA. The catalytic performances of bimetallic Ru–Co catalysts were improved with increasing Co loading due to the synergistic effect of Ru–Co alloying system together with the strong interaction between Ru and Co as revealed by XPS, H2-TPR, and TEM–EDX results. The enhancement of reducibility of Co oxides in the bimetallic Ru–Co catalysts led to higher hydrogenation activity with the Ru–0.6Co/TiO2 catalyst exhibited the best performances in FA selective hydrogenation of furfural to FA under the reaction conditions used.

tert-Butanol protection enables the chemoselective production of furfuryl alcohol directly from xylose over heteropolyacids using formic acid as a hydrogen honor.

Introduction of NiSO4 to Ni/SiO2 catalyst in hydrogenation of furfuryl alcohol: Tailoring metallic nickel sites to switch major product from tetrahydrofurfuryl alcohol to cyclopentanone

Alkyl levulinates have been identified as promising chemicals with various industrial applications. Here, a catalytic process for the synthesis in an n-butanol medium of n-butyl levulinate via the alcoholysis of biomass-derived furfuryl alcohol was performed using an extremely low concentration of sulfuric acid (≤ 0.01 M) as the catalyst. A study was conducted that was designed to optimize the process variables, which include acid concentration, reaction temperature, initial substrate concentration, and water content, as a function of time. The optimum conditions resulted in a furfuryl alcohol conversion of nearly 100% and a high n-butyl levulinate yield of up to 97%, which was confirmed by isolated yield. An advantage of this catalyst system is that negligible undesired oligomeric products were formed from the side reaction for the polymerization of furfuryl alcohol, the catalyst cost is low, and less solid waste was discharged from the neutralization of spent acid. Overall, this catalytic strategy is a facile, efficient, and economical approach to the conversion of biomass-derived furfuryl alcohol into alkyl levulinates.