Synthesis,characterization and conformational transitions in copolymers of 2‐(o‐chlorophenyl)‐4‐methylene‐1,3‐dioxolane with vinyl monomers

Copolymers of 2‐(o‐chlorophenyl)‐4‐methylene‐1,3‐dioxolane with methyl methacrylate and styrene were synthesized in benzene at 85 °C in the presence of 2,2′‐azobisisobutyronitrile as initiator. The structure of the resulting copolymers was investigated and a polymerization mechanism was proposed. The intrinsic viscosity of the copolymers in dilute solutions of carbon tetrachloride was determined as a function of temperature and conformational transitions were investigated. Copyright © 2004 Society of Chemical Industry     

Polycondensation of tetrachlorobisphenol a with chloromethylphosphonic dichloride. 1H-NMR kinetic study

The temperature-programmed polycondensation of tetrachlorobisphenol A with chloromethylphosphonic dichloride is carried out in the sample tube of an NMR spectrometer. From the spectra during polycondensation, the instantaneous concentration of components can be determined. Phosphorus and chlorine-containing polymers with flame-retardant properties are obtained.     

A multifactor study of catalyzed hydrolysis of solid NaBH4 on cobalt nanoparticles: Thermodynamics and kinetics

In the present work, hydrogen generation through hydrolysis of a NaBH_4(s)/catalyst_(s) solid mixture was realized for the first time as a solid/liquid compact hydrogen storage system using Co nanoparticles as a model catalyst. The performance of the system was analysed from both the thermodynamic and kinetic points of view and compared with the classical catalyzed hydrolysis of a NaBH₄ solution. The kinetic analysis of the NaBH_4(s)/catalyst_(s)/H₂O_(l) system shows that the reaction is first order with respect to the catalyst concentration, and the activation energy equal to 35 kJ mol_NaBH4⁻¹. Additionally, calorimetric measurements of the heat evolved during the hydrolysis of NaBH₄ solutions evidence the global process energy (−217 kJ mol_NaBH4⁻¹). Characterization of the cobalt nanoparticles before and after the hydrolysis associated with the calorimetric measurements suggests the “in situ” formation of a catalytically active Co_xB phase through “reduction” of an outer protective oxide layer that is regenerated at the end of reaction.     

Water molecular dynamics during bread staling by Nuclear Magnetic Resonance

Bread staling is a complex phenomenon that originates from multiple physico-chemical events (amylopectin retrogradation, water loss and redistribution) that are not yet completely elucidated. Molecular properties of white bread loaves were characterized by multiple proton Nuclear Magnetic Resonance (NMR) techniques (proton FID, T₂ and T₁ relaxation time) over 14 days of storage. Changes at a molecular level (faster decay of proton FIDs and shifting of proton T₂ relaxation times distributions towards shorter times), indicating a proton mobility reduction of the bread matrix, were observed during storage. Multiple ¹H T₂ populations were observed and tentatively associated to water-gluten and water-starch domains. Proton T₁ of bread was for the first time measured at variable frequencies (Fast Field Cycling NMR) and found to be strongly dependent upon frequency and to decrease in bread during storage, especially at frequencies ≤ 0.2 MHz. An additional proton T₁ population, relaxing at 2 ms, was detected at 0.52 MHz only at early storage times and tentatively attributed to a water-gluten domain that lost mobility during storage.     

Novel Data on the Polyphenol Composition of Italian Ancient Apple Cultivars

The pulp polyphenol composition of some Italian ancient apple cultivars, Dominici, Giachetta, Grigia di Torriana, Pom d'Aram, Ronzè, and Ros Borsetta, was studied in comparison with a Golden Delicious commercial variety, over a three-year period. Polyphenols were analyzed by liquid chromatography coupled with diode array and mass spectrometer detectors. The results showed that ancient varieties, such as Grigia di Torriana, Ros Borsetta, and Giachetta, constitute good sources of polyphenols, even without the peel. It was demonstrated that some representative apple phenolics, such as chlorogenic acid and phloridzin, were clearly affected by the harvesting year, whereas others, such as catechins and procyanidins, did not.     

Study of the effect of noble metal promotion in Ni-based catalyst for the Sabatier reaction

This paper reports the preparation and the evaluation of the performance of Ni-based powder catalysts with low nickel loading on the CO2 methanation reaction, that is an integral part of the power-to-gas (PtG) technology. CeO₂, CeZrO₄ and CeO₂/SiO₂ were selected as possible supports, and the results of this first screening pointed out that 10%Ni/CeO₂ catalyst could offer the best reaction performances because of ceria's peculiar characteristics. Moreover, the promotion of this promising formulation with the addition of a small amount of noble metals (Pt, Ru, Rh) was investigated, showing that platinum in particular can enhance the catalyst performances. A further study related to the noble metal loading pointed out that platinum and ruthenium have a different optimum loading condition: this result, together with the activity tests performed on monometallic formulations with only the noble metal, suggested that the two metals are able to catalyse two different reactions, thus promoting two different reaction mechanisms.     

Methane steam reforming in a Pd-Ag membrane reformer: An experimental study on reaction pressure influence at middle temperature

In this experimental work, methane steam reforming (MSR) reaction is performed in a dense Pd-Ag membrane reactor and the influence of pressure on methane conversion, CO_x-free hydrogen recovery and CO_x-free hydrogen production is investigated. The reaction is conducted at 450 °C by supplying nitrogen as a sweep gas in co-current flow configuration with respect to the reactants. Three experimental campaigns are realized in the MR packed with Ni-ZrO catalyst, which showed better performances than Ni-Al₂O₃ used in a previous paper dealing with the same MR system. The first one is directed to keep constant the total pressure in both retentate and permeate sides of the membrane reactor. In the second case study, the total retentate pressure is kept constant at 9.0 bar, while the total permeate pressure is varied between 5.0 and 9.0 bar. As the best result of this work, at 450 °C and 4.0 bar of total pressure difference between retentate and permeate sides, around 65% methane conversion and 1.2 l/h of CO_x-free hydrogen are reached, further recovering 80% CO_x-free hydrogen over the total hydrogen produced during the reaction. Moreover, a study on the influence of hydrogen-rich gas mixtures on the hydrogen permeation through the Pd-Ag membrane is also performed and discussed.