The catalytic cycloaddition of CO2 to epoxides to afford cyclic carbonates as useful monomers, intermediates, solvents, and additives is a continuously growing field of investigation as a way to carry out the atom-economic conversion of CO2 to value-added products. Metal-free organocatalytic compounds are attractive systems among various catalysts for such transformations because they are inexpensive, nontoxic, and readily available. Herein, we highlight and discuss key advances in the development of polymer-based organocatalytic materials that match these requirements of affordability and availability by considering their synthetic routes, the monomers, and the supports employed. The discussion is organized according to the number (monofunctional versus bifunctional materials) and type of catalytically active moieties, including both halide-based and halide-free systems. Two general synthetic approaches are identified based on the postsynthetic functionalization of polymeric supports or the copolymerization of monomers bearing catalytically active moieties. After a review of the material syntheses and catalytic activities, the chemical and structural features affecting catalytic performance are discussed. Based on such analysis, some strategies for the future design of affordable and readily available polymer-based organocatalysts with enhanced catalytic activity under mild conditions are considered.

ZnO nanostructures were synthesized by a combination of non-aqueous and aqueous sol-gel techniques to obtain morphologically different ZnO nanostructures, nanorods, and nanopyramids, featuring oxygen vacancies-rich exposed lattice faces and exhibiting different catalytic properties and activity. In particular, ZnO nanorods with high surface area (36 m2/g) were obtained through a rapid, scalable, and convenient procedure. The materials were tested for complete methane oxidation as an important benchmark reaction that is sensitive to surface area and to the availability of oxygen vacancies. Simple ZnO nanorods derived from nanosized quantum dots showed the best catalytic performance that compared well to that of several literature-reported perovskites, mixed metal oxides, and single-metal oxides in terms of T50 (576 °C) and T90 (659 °C) temperatures. Such a result was attributed to their high surface-to-volume ratio enhancing the availability of catalytically active sites such as oxygen vacancies whose abundance further increased following catalytic application at high temperatures. The latter effect allowed us to maintain a nearly stable catalytic performance with over 90% conversion for 12 h at 700 °C despite sintering. This research shows that ZnO-based nanomaterials with a high surface area are viable alternatives to oxides of commonly applied (but of potentially limited availability) transition metals (La, Mn, Co, Ni) for the complete combustion of methane when working at moderate temperatures (600–700 °C).