This work describes the use of simple zinc(II) salts (ZnCl₂, ZnCO₃, Zn(OAc)₂, ZnO, Zn(ClO₄)₂, Zn(TfO)₂, and Zn(BF₄)₂) as effective catalysts for the esterification of fatty acids with long-chain alcohols and simple polyols through a homogeneous system that allows the gradual and selective removal of water. The results show that the catalytic activity depends on the nature of the counterion: the most effective are the salts with poorly coordinating anions (perchlorate and triflate) or containing basic Brønsted anions (oxide, acetate, and carbonate). However, only with the latter is it possible to fully recover the catalyst at the end of each run, which is easily filtered in the form of zinc carboxylate, given its insolubility in the ester produced. In this way, it is possible to recycle the catalyst numerous times, without any loss of activity. This beneficial prerogative couples the efficiency of the homogeneous catalysis with the advantage of the heterogeneous catalysis. The process is, therefore, truly sustainable, given its high efficiency, low energy consumption, ease of purification, and the absence of auxiliary substances and byproducts.

An immobilization protocol of a model enzyme into silica nanoparticles was applied. This protocol exploited the use of the bifunctional molecule triethoxysilylpropylisocyanate (TEPI) for covalent binding through a linker of suitable length. The enzyme β-glucosidase (BG) was anchored onto wrinkled silica nanoparticles (WSNs). BG represents a bottleneck in the conversion of lignocellulosic biomass into biofuels through cellulose hydrolysis and fermentation. The key aspect of the procedure was the use of an organic solvent (anhydrous acetone) in which the enzyme was not soluble. This aimed to restrict its conformational changes and thus preserve its native structure. This approach led to a biocatalyst with improved thermal stability, characterized by high immobilization efficiency and yield. It was found that the apparent K_M value was about half of that of the free enzyme. The V_max was about the same than that of the free enzyme. The biocatalyst showed a high operational stability, losing only 30% of its activity after seven reuses.

The growing production of biodiesel as a promising alternative and renewable fuel led as the main problem the dramatic increase of its by-product: glycerol. Different strategies for glycerol derivatization have been reported so far, some more efficient or sustainable than others. Herein, we report a very promising and eco-friendly transformation of glycerol in nontoxic solvents and chemicals (i.e., solketal, ketals), proposing three new families of Fe(III) compounds capable of catalysing glycerol acetalization with unpublished turn over frequencies (TOFs), and adhering most of the principles of green chemistry. The comparison between the activity of complexes of formula [FeCl₃(1-R)] (1-R = substituted pyridinimine), [FeCl(2-R,R′)] (2-R,R′ = substituted O,O′-deprotonated salens) and their corresponding simple salts reveals that the former are extremely convenient because they are able to promote solketal formation with excellent TOFs, up to 10⁵ h^–1. Satisfactory performances were shown with respect to the entire range of substrates, with results being competitive to those reported in the literature so far. Moreover, the experimental activity was supported by an accurate and complete ab initio study, which disclosed the fundamental role of iron(III) as Lewis acid in promoting the catalytic activity. The unprecedented high activity and the low loading of the catalyst, combined with the great availability and the good eco-toxicological profile of iron, foster future applications of this catalytic process for the sustainable transformation of an abundant by-product in a variety of chemicals.