Promoting Effect of Ball Milling on the Functionalization and Catalytic Performance of Carbon Nanotubes in Glycerol Etherification.

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.

Upgrading Pyrolytic Residue from End-of-Life Tires to Efficient Heterogeneous Catalysts for the Conversion of Glycerol to Acetins.

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.

A Green Approach to Obtaining Glycerol Carbonate by Urea Glycerolysis Using Carbon-Supported Metal Oxide Catalysts.

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%MexOy/CFox) 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 CFox-supported ZnO and MgO systems. Screening of the reaction conditions was carried out by applying ZnO/CFox 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 CFox support on the process was noticed.

SO3H-functionalized carbon fibers for the catalytic transformation of glycerol to glycerol tert-butyl ethers.

Carbon fibers (CFs) of high quality were produced from hydrocarbons such as isobutane or ethylene using the catalytic chemical vapor deposition method (CCVD) and Ni catalyst. The as-prepared samples were functionalized with acidic groups using concentrated sulfuric acid or 4-benzenediazonium sulfonate (BDS) generated in situ from sulfanilic acid and sodium nitrite. The morphological features of the materials were confirmed by transmission electron microscopy, whereas their physicochemical properties were characterized by means of elemental and textural analyses, thermogravimetric (TG) method, Raman spectroscopy, potentiometric back titration, and X-ray diffraction analysis. The obtained CFs were used as catalysts in glycerol etherification with tert-butyl alcohol at 110 °C under autogenous pressure. The BDS-modified CFs were particularly effective in the reaction, showing high glycerol conversions (of about 45-55% after 6 h) and substantial yields of mono- and di-glycerol ethers. It was found that the chemistry of the sample surface was crucial for the process. The high concentration of -SO3H groups decorating CFs boosted the formation of di- and tri-tert-butyl glycerol ethers. Surface oxygen functionalities also had a positive effect on the reaction, however, their impact on the catalytic performances of CFs was significantly weaker compared to that shown by -SO3H groups and it was probably due to the adsorption of reagents on the catalyst surface.

Production of valuable chemicals from glycerol using carbon fiber catalysts derived from ethylene.

Ethylene was thermocatalytically transformed into carbon products via a CCVD process. The filamentous carbon obtained was further modified with concentrated sulfuric acid or 4-benzenediazonium sulfonate (BDS) to produce acid-type catalysts. The as-prepared samples were characterized by SEM and TEM techniques to confirm their morphological features. TG, XRD, elemental, and porosity analyses were also performed to assess the quality of these materials. The fabricated carbons were tested in eco-friendly green synthesis of value-added fuel bio-additives, namely in glycerol esterification. The reaction of glycerol transformation was performed with acetic acid at 80 °C using different glycerol to acetic acid (Gly/AA) molar ratios. The samples functionalized with diazonium salt showed better performance in the above process than those modified with H2SO4, and this was found to be directly related to the degree of surface functionalization with acidic sites. BDS-modified carbon fibers allowed obtaining acceptable results within 6 h when the reaction was performed with a Gly/AA molar ratio of 1:6, however, the dominant products in this case were mono- and diacetins. Extended reaction time altered the distribution of products. Finally, the combined selectivity to the targeted acetins (i.e., DA and TA) was about 75.5%. A direct correlation between the content of -SO3H groups of CNFs and the yield of higher acetins was found.

Impact of Thermal Treatment of Nb2O5 on Its Performance in Glucose Dehydration to 5-Hydroxymethylfurfural in Water.

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.