In the present work, two sets of the Co/ZSM-5 mesoporous catalysts with different acidity and Co loadings varying from 1 to 5 and 10 wt% were prepared using mesoporous ZSM-5-A (Si/Al = 50) and ZSM-5-B (Si/Al = 150) as support. X-ray diffraction (XRD) analysis showed that the Co₃O₄ phase was formed in the surface of catalysts and the reducibility of Co₃O₄ nanoparticles on the ZSM-5-B was greater in comparison with that on the ZSM-5-A solid. In situ FTIR of pyridine adsorption characterization confirmed that all of the Co/ZSM-5 catalysts contained both Lewis (L) and Brønsted (B) acid sites, with a relatively balanced B/L ratio ranging from 0.61 to 1.94. Therefore, the Si/Al molar ratio in ZSM-5 affected both the surface acidity and the cobalt oxide reducibility. In the esterification of unsaturated omega-9 oleic acid with methanol, under the optimal reaction conditions (temperature 160 °C, catalyst concentration 2 g/L, methanol/oleic acid molar ratio 30, and reaction time 180 min), the biodiesel selectivity reached 95.1% over the most active 10 wt% Co/ZSM-5-B catalyst. The higher esterification activity of the Co/ZSM-5-B catalysts can be correlated with the greater amount of B and L acid sites, the balanced B/L ratio, and the higher reducibility of Co₃O₄ nanoparticles. The oleic acid esterification reaction followed the bifunctional mechanism of combining metal function (dispersed Co₃O₄ with a greater reducibility) with the acidity function (both B and L acid sites with a relative balanced B/L ratio) on the catalysts, which may help in providing a deep understanding of the esterification pathways and benefiting the design of novel bifunctional catalysts for biofuel production.

This work reports the results of the ultrasound-assisted hydrothermal synthesis of two sets of V₂O₅ dispersed on SBA-15 and Zr doped SBA-15 catalysts used for the oxidation of dibenzothiophene (DBT) in a model diesel via the combination of oxidation, catalysis, and extraction technical route. These catalysts contained Lewis acidity as major and Brønsted acidity as minor. The amount of acidity varied with the content of vanadia and zirconium doping. It was found that DBT conversion is very sensitive to the Lewis acidity. DBT conversion increased by increasing the vanadium content and correlated well with the amount of surface Lewis acidity. Under the optimal experimental condition (Reaction temperature: 60 °C, reaction time 40 min, catalyst concentration: 1 g/L oil; H₂O₂/DBT mole ratio = 10), the 30% V₂O₅/SBA-15 and 30% V₂O₅/Zr-SBA-15 catalysts could convert more than 99% of DBT. Two reaction pathways of DBT oxidation involving vanadia surface structure, Lewis acidity, and peroxometallic complexes were proposed. When the vanadia loading V₂O₅ ≤ 10 wt%, the oxidative desulfurization (ODS) went through the Pathway I; in the catalysts with moderate vanadia content (V₂O₅ = 20–30 wt%), ODS proceeded via the Pathways II or/and the Pathway I.

We report the simultaneous production of hydrogen fuel and carbon nanotubes (CNTs) via methane dehydrogenation catalyzed with Ni/SBA-15. Most Ni nanoparticles (NPs) with size between 10 and 30 nm were highly dispersed on SBA-15 and most of them had a strong interaction with the support. At temperatures ranging from 500 to 800 °C, methane could be decomposed to release hydrogen with 100% selectivity at conversion between 51 and 65%. There was no CO or CO₂ detectable in the reaction fluent. In the initial stage of the reaction, amorphous carbon and dehydrogenated methane species adsorbed on the Ni NPs promoted the CH₄ decomposition. The amorphous carbon atoms were then transformed into carbon nanotubes which chiefly consisted of a multiwall structure and grew towards different orientations via a tip-growth or a base-growth modes, controlled by the interaction strength between the Ni NPs and the SBA-15 support. Reaction temperature affected not only methane conversion, but also the diffusion of carbon atoms on/in the Ni NPs and their precipitation at the interfaces. At higher temperature, bamboo-like CNTs or onion-like metal-encapsulated carbons were formed, mainly due to the rate of carbon atom formation greater than that of carbon precipitation for CNTs construction. The CNTs formation mechanisms are discussed and their growth modes under different conditions are proposed.

Various Keggin-type heteropolyoxometalate catalysts with structural defects and surface acidity were synthesized by immobilizing 12-phosphotungstic acid (HPW) on mesoporous SBA−15, to produce near-zero-sulfur diesel fuel. As the calcination temperature increased, the W=O and the corner-shared W–O–W bonds in the Keggin unit partially broke, creating oxygen defects, as evidenced by the Rietveld refinement and in situ FTIR characterization. All the catalysts contained Lewis (L) and Brønsted (B) acid sites, with L acidity predominant. The relative intensity of the IR band (I₉₈₀) of W=O bond inversely correlated with the number of L acid sites as the calcination temperature varied, suggesting that oxygen defects contributed to the Lewis acid sites formation. In the oxidation of dibenzothiophene (DBT) in a model diesel within a biphasic system, DBT conversion exceeded 99% under the optimal reaction conditions (reaction temperature 70 °C, reaction time 60 min, H₂O₂/sulfur molar ratio 8, H₂O₂/formic acid molar ratio 1.5, catalyst concentration 2 mg/mL). The influence of fuel composition and addition of indole and 4,6-DMDBT on DBT oxidation were also evaluated. Indole and cyclohexene negatively impacted the DBT oxidative removal. Oxygen defects served as active centers for competitive adsorption of sulfur compound and oxidant. Both L and B acid sites were involved in transferring O atom from peroxophosphotungstate complex to sulfur in DBT, resulting in DBTO₂ sulfone, which was immediately extracted by polar acetonitrile. This study confirms that structural defects and surface acidity are crucial in the deep oxidative desulfurization (ODS) reaction, and in enabling the simultaneous oxidation and separation of refractory organosulfur compounds in a highly efficient model diesel.

A high-performance and scalable lipase immobilization method using a dipping and jet break-up technique was reported for the production of microcapsule biocatalysts with an entrapped cascade of lipase enzyme. The lipase from Candida antarctica (CALb) recombinant Aspergillus oryzae and from the vegetal of Jatropha curcas L. (var. Sevangel) in Morelos State of Mexico were entrapped by mixing with a sodium alginate biopolymer at different concentrations. The obtained microcapsules were hardened in a CaCl₂ solution, aiming at developing Ca²⁺ alginate microbeads with sizes mostly from 220 to 300 μm. The relationship between the process variables with the shape and size of the alginate drops before and after the gelation was established with aid of optical image analysis. The results showed that a critical Ohnesorge number (Oh) > 0.24 was required to form spherical microencapsulated beads. The biodiesel production via esterification/transesterification reaction was performed using the crude Jatropha curcas L. oil as feedstock in a batch reactor using lipase microcapsules as biocatalysts. Under the optimal reaction condition (ethanol-to-oil mass ratio: 10; water content 9.1 wt%, microencapsulated biocatalyst mass: 5.25 g, reaction temperature: 35 °C, pH of reaction mixture 7.5, stirring force 6 g), an approximately 95% fatty acid ethyl esters (FAEE) yield could be obtained. The biodiesel obtained from this work completely satisfied with the related ASTM D6751 and EN14214 standards. The microencapsulation technique reported herein allows the production of lipase microcapsules on a continuous large scale with the characteristics required for sustainable biofuel production and it can be also applied in other fields such as food processing and the pharmaceutical industry.