Starting from the environmental issues related to global warming, climate change and reduction of greenhouse gas emissions, this review paper describes how CO₂ recycling can represent a challenging strategy suitable to explore new concepts and opportunities for catalytic and industrial development. In this view, the production of dimethyl ether (DME) from catalytic hydrogenation of CO₂ appears as a viable technology, able to meet also the ever-increasing need for alternative environmentally-friendly fuels and energy carriers. Basic considerations on thermodynamic aspects controlling DME production from CO₂ are presented, then summarizing the main catalytic systems developed in such a field. Special attention is paid on the role assumed during last years by zeolite-based systems, either in the methanol-to-DME dehydration step or in the one-pot CO₂-to-DME hydrogenation. On the whole, the productivity of DME results significantly to be dependent on several catalyst features, linked not only to the metal-oxide phase responsible for CO₂ activation/hydrogenation, but also to specific properties of the zeolites (i.e., topology, porosity, surface area, acidity, interaction with active metals, distributions of metal particles, …) influencing activity and stability of hybridized bifunctional heterogeneous catalysts.

It is of great significance to develop sustainable processes of catalytic reaction. We report an efficient and selective procedure for the synthesis of acetylated bioactive compounds in water. The use of 1-acetylimidazole combined with Er(OTf)₃ as Lewis acid catalyst gives high regioselectivity and good to excellent yields for the acetylation of primary hydroxyl groups as well as amino groups. The protection is achieved in short reaction times under microwave irradiation and is successful even in the case of base-sensitive substrates.

On June 8 and June 9, 2017, we gave two invited lectures at the Zelinsky Institute of Organic Chemistry (ZIOC) of the Russian Academy of Sciences, Moscow. The first lecture, “Sol-Gel Catalysts: Making Green Chemistry Possible”, focused on the practical outcomes of 25 years of research on sol-gel entrapped catalysts. The second, “Chemistry for the Bioeconomy: From Discussion to Action”, offered a critical insight to the forthcoming bioeconomy. Both lectures aroused much interest in the audience and ended with a vigorous discussion lasting about one hour. An outlook is provided herein.

Phosphorylation reactions of glycerol were studied using different inorganic phosphates such as sodium phosphate, trimetaphosphate (a condensed phosphate), and struvite. The reactions were carried out in two non-aqueous solvents: formamide and a eutectic solvent consisting of choline chloride and glycerol in a ratio of 1:2.5. The glycerol reacted in formamide and in the eutectic solvent with phosphate to yield its phosphorylated derivatives in the presence of silicates such as quartz sand and kaolinite clay. The reactions were carried out by heating glycerol with a phosphate source at 85 °C for one week and were analyzed by 31P nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS). The yield of the phosphorylated glycerol was improved by the presence of silicates, and reached 90% in some experiments. Our findings further support the proposal that non-aqueous solvents are advantageous for the prebiotic synthesis of biomolecules, and suggest that silicates may have aided in the formation of organophosphates on the prebiotic earth.

Synergistic effects between reactions, reagents and catalysts can lead to minor heats of reaction and occur as an inherent result of multi-component reactions (MCRs) and their extensions. They enable syntheses to be performed at a low energy level and the number of synthesis steps to be drastically reduced in comparison with ‘classical’ two-component reactions. The very high potential for variability, diversity and complexity of MCRs additionally generates an extremely diverse range of products, thus bringing us closer to the aim of being able to produce tailor-made and extremely low-priced materials, drugs and libraries.