Transformation of carbon dioxide to diethyl carbonate over ceria and ceria-supported catalysts

Carbon dioxide is regarded, nowadays, as a primary anthropogenic greenhouse gas leading to global warming. Hence, chemical fixation of CO2 has attracted much attention as a possible way to manufacture useful chemicals. One of the most interesting approaches of CO2 transformations is the synthesis of organic carbonates. Since conventional production technologies of these compounds involve poisonous phosgene and carbon monoxide, there is a need to develop novel synthetic methods that would better match the principles of "Green Chemistry" towards protection of the environment and human health. Over the years, synthesis of dimethyl carbonate was under intensive investigation in the academia and industry. Therefore, this study was entirely directed towards equally important homologue of carbonic esters family namely diethyl carbonate (DEC). Novel synthesis method of DEC starting from ethanol and CO2 over heterogeneous catalysts based on ceria (CeO2) was studied in the batch reactor. However, the plausible drawback of the reaction is thermodynamic limitations. The calculated values revealed that the reaction is exothermic (ΔrHØ298K = ─ 16.6 J/ ) and does not occur spontaneously at rooms temperature (ΔrGØ 298K = 35.85 kJ/mol). Moreover, co-produced water easily shifts the reaction equilibrium towards reactants excluding achievement of high yields of the carbonate. Therefore, in-situ dehydration has been applied using butylene oxide as a chemical water trap. A 9-fold enhancement in the amount of DEC was observed upon introduction of butylene oxide to the reaction media in comparison to the synthetic method without any water removal. This result confirms that reaction equilibrium was shifted in favour of the desired product and thermodynamic boundaries of the reaction were suppressed by using butylene oxide as a water scavenger. In order to obtain insight into the reaction network, the kinetic experiments were performed over commercial cerium oxide. On the basis of the selectivity/conversion profile it could be concluded that the one-pot synthesis of diethyl carbonate from ethanol, CO2 and butylene oxide occurs via a consecutive route involving cyclic carbonate as an intermediate. Since commercial cerium oxide suffers from the deactivation problems already after first reaction cycle, in-house CeO2 was prepared applying room temperature precipitation technique. Variation of the synthesis parameters such as synthesis time, calcination temperature and pH of the reaction solution turned to have considerable influence on the physico-chemical and catalytic properties of CeO2. The increase of the synthesis time resulted in high specific surface area of cerium oxide and catalyst prepared within 50 h exhibited the highest amount of basic sites on its surface. Furthermore, synthesis under pH 11 yielded cerium oxide with the highest specific surface area, 139 m2/g, among all prepared catalysts. Moreover, CeO2─pH11 catalyst demonstrated the best catalytic activity and 2 mmol of DEC was produced at 180 oC and 9 MPa of the final reaction pressure. In addition, ceria-supported onto high specific surface area silicas MCM-41, SBA-15 and silica gel were synthesized and tested for the first time as catalysts in the synthesis of DEC. Deposition of cerium oxide on MCM-41 and SiO2 supports resulted in a substantial increase of the alkalinity of the carrier materials. Hexagonal SBA-15 modified with 20 wt % of ceria exhibited the second highest basicity in the series of supported catalysts. Evaluation of the catalytic activity of ceria-supported catalysts showed that reaction carried out over 20 wt % CeO2-SBA-15 generated the highest amount of DEC.

I volontari italiani nelle Waffen-SS. Il pensiero politico, la formazione culturale e le motivazioni al volontariato. Una storia orale

My doctoral dissertation examines the experiences of the Italian volunteers in the Waffen-SS troops using in-depth interviews with former volunteers as the main primary source. This phenomenon, even if significant in size (depending on the source, some 15 000-20 000 Italian men volunteered in the Waffen-SS), has been hitherto largely unknown to historical research. The available literature on the Italian volunteers, mainly written by military history enthusiast journalists and methodologically weak, concentrates mainly on the combat operations and military organization, and offers a rather stereotypical profile of the volunteers. My dissertation does not aim to reconstruct the military history of the different divisions of the Waffen-SS in which Italian volunteers operated but instead to examine the subjective, private and intimate experience of the volunteers in order to understand the motivations, attitudes, beliefs and cultural and family background, as well as their political ideas. The main objective of my doctoral dissertation is to discover the ideological precepts of the volunteers’ political credo. As the last phase of fascism and its ideology, often defined as the “Germanisation” or “Nazification” of fascism, is still the object of wide academic debate, a better understanding of the volunteers’ ideology also contributes to deepening overall knowledge of the nature of this last phase. The theoretical frame of my dissertation lies in oral history, in particular in the postmodernist approach to oral history, through which I reconstruct the volunteers’ ideology. In-depth interviews with former volunteers are the main primary source, but multiple data collection methods have been adopted. Phone interviews and correspondence with the volunteers have also been considered as primary sources. In addition to interviews and correspondence, family archives consisting of diaries, correspondence with the volunteers’ relatives and photographic material have also been collected and examined. An ethnographic observation of the volunteers’ domestic spaces has been conducted during the in-depth interviews, and photo self-elicitation techniques have been used in cases where the volunteers were willing to share their photographs. An exhaustive portrait of the ideological structure of the volunteers has been obtained, as well as of the cultural and social origins of the values that contributed to the rise and adoption of this ideology. Further, the volunteers’ motivations to enlist have been clearly reconstructed, together with their cultural, political, social and military backgrounds. The results of the research are particularly relevant both for comprehension of the Italian phenomenon of volunteering in the Waffen-SS and for the reconstruction of the ideological dynamics of the last phase of fascism. The volunteers’ political and ideological system, which can be defined as the Italian SS-fascist ideology, disagrees strongly with the vaguely described ideological profile offered by previous studies that describe volunteers as generically “super-fascist”. The research also offers the opportunity for a deeper understanding of the final fascist ideological trajectory, currently defined, not without a certain level of approximation, as the “Germanisation” or “Nazification” of fascist ideology.

Bonvenon al Finnlando

kuv., 15 x 24 cm