Determination of the nature of the Cu coordination complexes formed in the presence of NO and NH3 within SSZ-13

Ammonia-selective catalytic reduction (NH3-SCR) using Cu zeolites is a well-established strategy for the abatement of NOx gases. Recent studies have demonstrated that Cu is particularly active when exchanged into the SSZ-13 zeolite, and its location in either the 6r or 8r renders it an excellent model system for fundamental studies. In this work, we examine the interaction of NH3-SCR relevant gases (NO and NH3) with the Cu2+ centers within the SSZ-13 structure, coupling powder diffraction (PD), X-ray absorption spectroscopy (XAFS), and density functional theory (DFT). This combined approach revealed that, upon calcination, cooling and gas exposure Cu ions tend to locate in the 8r window. After NO introduction, Cu-ions are seen to coordinate to two framework oxygens and one NO molecule, resulting in a bent Cu-nitrosyl complex with a Cu-N-O bond angle of similar to 150 degrees. Whilst Cu seems to be partially reduced/changed in coordination state, NO is partially oxidized. On exposure to NH3 while the PD data suggest the Cu2+ ion occupies a similar position, simulation and XAFS pointed toward the formation of a Jahn-Teller distorted hexaamine complex [Cu(NH3)(6)](2+) in the center of the cha cage. These results have important implications in terms of uptake and storage of these reactive gases and potentially for the mechanisms involved in the NH3-SCR process

Does dehydration alter the success rate and technique of three-point shooting in elite basketball?

In order to better inform the effects of dehydration and hydration guidelines, we tested the acute effects of a 2% dehydration protocol on performance and technique of 3-point shooting (3PS) in Elite Basketball players (n = 9). The 3PS technique was monitored by using nanotechnology inertial measurement units positioned onto body joints during the exercise. When dehydrated (−2.1% ± 0.5% of body mass), 7 players experienced a slight decrease (−10.0% ± 19.6%, p = 0.16) in success rate, while RPE increased from 9.1 ± 2.6 to 13.0 ± 2.5 in euhydrated (EUH) and dehydrated (DEH) condition respectively (p = 0.003). DEH slightly altered the 3PS technique as the knee angle increased (p = 0.02) at toe-off time and the hip angle decreased during the 3PS (p = 0.01). The speed of ball release tended to be increased (p = 0.05) in DEH compared to EUH. Data from this study suggest that a 2% dehydration is tolerable for elite Basketball players, although a stronger dehydration might accentuate the effects observed

Syndioselective ring-opening polymerization and copolymerization of trans-1,4-cyclohexadiene carbonate mediated by achiral metal- and organo-catalysts

International audienceThe ring-opening polymerization (ROP) of trans-1,4-cyclohexadiene carbonate (CHDC) has been investigated computationally and experimentally. DFT computations indicate that ring-opening of CHDC is thermodynamically possible, yet to a lesser extent than that of trans-cyclohexene carbonate (CHC). Effective homopolymerizations of rac-CHDC and simultaneous or sequential copolymerizations of rac-CHDC with rac-CHC and L-LA were achieved with a diaminophenolate zinc-based complex ([(NNO)ZnEt]) or a guanidine (TBD) associated with an alcohol. These ROP reactions, which confirmed the lower reactivity of rac-CHDC vs. rac-CHC, especially in homopolymerization, proceeded without any decarboxylation. Quite uniquely, highly syndiotactic PCHDC was obtained from ROP of rac-CHDC with both the zinc- and TBD-based catalysts, as revealed by 13C{1H} NMR studies. The prepared homopolymers and block or random copolymers were characterized by 1H, 13C{1H} NMR, MALDI-ToF MS, SEC and DSC techniques

Pedogenesis and carbon sequestration in transformed agricultural soils of Sicily

The increasing atmospheric CO2 concentration is a consequence of human activities leading to severe environmental deteriorations. Techniques are thus needed to sequester and reduce atmospheric carbon. One of the proposed techniques is the transformation or construction of new soils into which more organic carbon can be sequestered and CO2 be consumed by increased weathering. By using a chronosequence of new and transformed soils on crushed limestone (0–48 years) in a Mediterranean area (Sicily), we tried to quantify the amount of organic carbon that could be additionally sequestered and to derive the corresponding rates. A further aim was to trace chemical weathering and related CO2 consumption and the evolution of macropores that are relevant for water infiltration and plant nutrition. Owing to the irrigation of the table grape cultivation, the transformed soils developed fast. After about 48 years, the organic C stocks were near 12 kg m−2. The average org. C sequestration rates varied between 68 and 288 g m−2 yr−1. The C accumulation rates in the transformed soils are very high at the beginning and tend to decrease over (modelled) longer time scales. Over these 48 years, a substantial amount of carbonate was leached and reprecipitated as secondary carbonates. The proportion of secondary carbonates on the total inorganic carbon was up to 50%. Main mineralogical changes included the formation of interstratified clay minerals, the decrease of mica and increase of chloritic components as well as goethite. The atmospheric CO2 consumption due to silicate weathering was in the range of about 44–72 g C m−2 yr−1. Due to the high variability, the contribution of chemical weathering to CO2 consumption represents only an estimate. When summing up organic C sequestration and CO2 consumption by silicate weathering, rates in the order of 110–360 g C m−2 yr−1 are obtained. These are very high values. We estimated that high sequestration and CO2 consumption rates are maintained for about 50–100 years after soil transformation. The macropore volume decreased over the observed time span to half (from roughly 10 to 5 %). The transformation of soils may even amend their characteristics and increase agricultural production. Due to the relatively sandy character, enough macropores were present and no substantial compaction of the soils occurred. However, great caution has to be taken as such measures can trigger deterioration of both soil ecosystem services and soil quality