Acetylation of glycerol to yield monoacetin (MAT), diacetin (DAT), and triacetin (TAT) over NiO-supported CeO2 (xNiO/CeO2) catalysts is reported. The catalysts were synthesized utilizing a sol-gel technique, whereby different quantities of NiO (x = 9, 27, and 45 wt%) were supported onto the CeO2 substrate, and hexadecyltrimethylammonium bromide (CTABr) served as a porogen. The utilization of EDX elemental mapping analysis confirmed the existence of evenly distributed Ni2+ ion and octahedral NiO nanoparticles on the CeO2 surface through the DRS UV-Vis spectroscopy. The most active catalyst is 27NiO/CeO2 based on TAT selectivity in the glycerol acetylation with ethanoic acid, attaining 97.6% glycerol conversion with 70.5% selectivity to TAT at 170 °C with a 1:10 glycerol/ethanoic acid molar ratio for 30 min using a non-microwave instant heating reactor. The 27NiO/CeO2 is reusable without significant decline in catalytic performance after ten consecutive reaction cycles, indicating high structure stability with accessible active acidity.
It is essential to investigate the physicochemical and thermal properties of choline chloride (ChCl)-based deep eutectic solvents (DESs) as hydrogen bond acceptor (HBA) with various hydrogen bond donor (HBD) functional groups, such as α-hydroxy acid (lactic acid) or polyol (glycerol). It is important to consider how molar ratios impact these properties, as they may be altered for particular applications. This study aimed to examine the physicochemical and thermal properties of ChCl-based DESs with lactic acid (LA) or glycerol (Gly) at different molar ratios (1:2-1:10). The pH of ChCl:LA (0-1.0) is lower than that of ChCl:Gly (4.0-5.0) because of the hydrogen bonds between ChCl and LA. A higher amount of LA/Gly resulted in higher densities of ChCl:Gly (1.20-1.22 g cm-3) and ChCl:LA (1.16-1.19 g cm-3) due to the stronger hydrogen bonds and tighter packing of the molecules. The refractive index of ChCl:Gly (1.47-1.48) was higher than ChCl:LA (1.44-1.46), with a trend similar to density. The viscosities of ChCl:Gly (0.235-0.453 Pa s) and ChCl:LA (0.04-0.06 Pa s) increased with increasing LA/Gly molar ratio but decreased with temperature due to the high kinetic energy from heating, lowering the attractive forces between molecules. The activation energy for ChCl:LA (15.29-15.55 kJ mol-1) is greater than for ChCl:Gly (7.77-8.78 kJ mol-1), indicating that ChCl:LA has a greater viscosity-temperature dependence than ChCl:Gly. The DESs decomposition temperatures are 179.73-192.14 °C for ChCl:LA and 189.69-197.41 °C for ChCl:Gly. Freezing temperatures are correlated with the molecular weight of HBDs, with lower values causing a larger decrease in freezing temperatures. The interactions of polyols with anions were stronger than those of α-hydroxy acids with anions. The variations in HBA to HBD molar ratios affected DESs properties, providing a fundamental understanding of the properties critical for their diverse applications.