The cascade dehydration of glucose to 5-hydroxymethylfurfural (HMF) was carried out in water over a series of Nb₂O₅ catalysts, which were derived from the thermal treatment of niobic acid at 300 and 550 °C, under air or inert atmosphere. Amorphous niobic acid showed high surface area (366 m²/g) and large acidity (2.35 mmol/g). With increasing the temperature of the thermal treatment up to 550 °C, the amorphous Nb₂O₅ was gradually transformed into a pseudohexagonal phase, resulting in a decrease in surface area (27–39 m²/g) and total acidity (0.05–0.19 mmol/g). The catalysts’ performance in cascade dehydration of glucose realized in pure water was strongly influenced by the total acidity of these materials. A remarkable yield of 37% HMF in one-pot reaction in water was achieved using mesoporous amorphous niobium oxide prepared by thermal treatment of niobic acid at 300 °C in air. The best-performing catalyst displayed a total acidity lower than niobic acid (1.69 mmol/g) which afforded a correct balance between a high glucose conversion and limited further conversion of the target product to numerous polymers and humins. On the other hand, the treatment of niobic acid at 550 °C, independently of the atmosphere used during the sample preparation (i.e., air or N₂), resulted in Nb₂O₅ catalysts with a high ratio of Lewis to Brønsted acid sites and poor total acidity. These materials excelled at catalyzing the isomerization step in the tandem process.

The results of sustainable and selective synthesis of glycerol carbonate (GC) from urea and glycerol under ambient pressure using carbon-fiber-supported metal oxide catalysts are reported. Carbon fibers (CF) were prepared via a catalytic chemical vapor deposition method (CCVD) using Ni as a catalyst and liquefied petroleum gas (LPG) as a cheap carbon source. Supported metal oxide catalysts were obtained by an incipient wetness impregnation technique using Zn, Ba, Cr, and Mg nitrates. Finally, the samples were pyrolyzed and oxidized in an air flow. The obtained catalysts (10%Me_xO_y/CF_ox) were tested in the reaction of urea glycerolysis at 140 °C for 6 h under atmospheric pressure, using an equimolar ratio of reagents and an inert gas flow for NH₃ removal. Under the applied conditions, all of the prepared catalysts increased the glycerol conversion and glycerol carbonate yield compared to the blank test, and the best catalytic performance was shown by the CF_ox-supported ZnO and MgO systems. Screening of the reaction conditions was carried out by applying ZnO/CF_ox as a catalyst and considering the effect of reaction temperature, molar ratio of reagents, and the mode of the inert gas flow through the reactor on the catalytic process. Finally, a maximum yield of GC of about 40%, together with a selectivity to glycerol carbonate of ~100%, was obtained within 6 h of reaction at 140 °C using a glycerol-to-urea molar ratio of 1:1 while flowing Ar through the reaction mixture. Furthermore, a positive heterogeneous catalytic effect of the CF_ox support on the process was noticed.

A facile and eco-friendly approach using in situ-generated 4-benzenediazonium sulfonate (BDS) was applied to prepare highly functionalized carbon nanotubes (CNTs). The effectiveness of this functionalization was additionally enhanced by a green and short-time ball milling process applied beforehand. The obtained BDS-modified CNTs presented significant activity in glycerol etherification, producing tert-butyl glycerol ethers, which are considered promising fuel additives. Excellent results of ~56% glycerol conversion and ~10% yield of higher-substituted tert-butyl glycerol ethers were obtained within just 1 h of reaction at 120 °C using a low catalyst loading of only 2.5 wt.%. Furthermore, the sulfonated CNTs were reusable over several reaction cycles, with only a minor decrease in activity. Additionally, the sample activity could be restored by a simple regeneration approach. Finally, a clear correlation was found between the content of -SO₃H groups on the surface of CNTs and the catalytic performances of these materials in glycerol etherification. Improved interaction between functionalized ball-milled CNTs and the reactants was also suggested to positively affect the activity of these catalysts in the tested process.

Recovered carbon blacks (rCBs) produced from end-of-life tires using pyrolysis were transformed into solid acid catalysts for the synthesis of acetins, i.e., products with a wide spectrum of practical applications. Tuning the chemical properties of the surface of samples and introducing specific functional groups on the rCBs were achieved through carbon functionalization with concentrated H₂SO₄. The initial and modified rCBs were thoroughly characterized using techniques such as elemental analysis, potentiometric back titration, thermogravimetric technique, scanning and transmission microscopy, X-ray photoelectron spectroscopy, etc. The catalytic activities of the samples were measured via batch mode glycerol acetylation performed at 110 °C and compared to the catalytic performance of the functionalized commercial carbon black. The modified rCBs were found to show a significant catalytic effect in the tested reaction, giving high glycerol conversions (above 95%) and satisfactory combined yields of diacetins and triacetin (~72%) within 4 h; this behavior was attributed to the presence of -SO₃H moieties on the surface of functionalized rCBs. The reusability tests indicated that the modified samples were catalytically stable in subsequent acetylation runs. The obtained results evidenced the feasibility of using end-of-life tires for the production of effective acid catalysts for glycerol valorization processes.

High-purity and technical-grade carbon nanotubes (CNTs) were functionalized and compared, for the first time applying various mechanochemical methods to endow their surfaces with strongly acidic features. The as-prepared samples were used as catalysts in glycerol etherification performed with tert-butyl alcohol at 110 °C under autogenous pressure, converting glycerol to glycerol tert-butyl ethers, i.e., important fuel additives, in a green way. The best-performing catalyst was the CNT sample ball-milled with glucose and hydrothermally treated with fuming H₂SO₄, which showed a 52.4% glycerol conversion just after 6 h. The catalytic performance of the sample was ascribed to its improved functionalization when using glucose which worked as a “binding agent” for the active functional groups, facilitating the grafting of the –SO₃H sites on the CNT surface in a relatively short time and at a low temperature of modification. Furthermore, it was found that acidic oxygen functionalities, co-introduced with sulfonic groups during the modification, cooperated with –SO₃H sites and jointly worked to enhance the CNT activity in glycerol etherification. Finally, it was shown that adequately tailored technical-grade CNTs could act as promising and much cheaper solid acids than functionalized expensive high-purity CNTs typically used for industrial applications.