CO2 is considered to play a key role in an eventual climate change, due to its accumulation in the atmosphere. The control of its emission represents a challenging task that requires new ideas and new technologies. The use of perennial energy sources and renewable fuels instead of fossil fuels and the conversion of CO2 into useful products are receiving increased attention. The utilization of CO2 as a raw material for the synthesis of chemicals and fuels is an area in which scientists and industrialists are much involved: the implementation of such technology on a large scale would allow a change from a linear use of fossil carbon to its cyclic use, mimicking Nature. In this paper the use of CO2 as building block is discussed. CO2 can replace toxic species such as phosgene in low energy processes, or can be used as source of carbon for the synthesis of energy products. The reactions with dihydrogen, alcohols, epoxides, amines, olefins, dienes, and other unsaturated hydrocarbons are discussed, under various reaction conditions, using metal systems or enzymes as catalysts. The formation of products such as formic acid and its esters, formamides, methanol, dimethyl carbonate, alkylene carbonates, carbamic acid esters, lactones, carboxylic acids, and polycarbonates, is described. The factors that have limited so far the conversion of large volumes of CO2 are analyzed and options for large‐scale CO2 catalytic conversion into chemicals and fuels are discussed. Both homogeneous and heterogeneous catalysts are considered and the pros and cons of their use highlighted. © 2013 Society of Chemical Industry

Rocking chair enzyme: Chemical reducing agents (sodium dithionite) or bioglycerol (as H and e−‐donor under irradiation in the presence of ZnS‐A as photocatalyst) are able to back‐convert NADP+ into NADPH, which is used as e−‐donor in the enzymatic reduction of CO2 into CH3OH. In doing so, the molar ratio CH3OH/CO2 has been increased (without recycling of NADP+) using the photocatalyst.

Aqueous glycerol was used as the hydrogen source for the reduction of CO(2) to the hydrogen carrier formic acid in the presence of the catalyst [RuCl(2)(PPh(3))(3)]. All intermediates were identified and characterized. Glycerol was converted into glycolic acid, HO-CH(2)-COOH, that was identified by using (1)H and (13)C NMR spectroscopy.