Syntheses of chromium tricarbonyl organometals of 1-methyl-naphthalene and different polycyclic aromatic hydrocarbons,characterisation of the (C11H10)Cr(CO)3 isomers and the crystal structure of the [(η6-5,6,7,8,9,10-C11H10)Cr(CO)3] complex

The synthesis of organometal complexes from chromium hexacarbonyl with 1-methyl-naphthalene ligand is reported. Two arene-chromium-tricarbonyl isomers are formed at competitive yields, featured with the metal fragment coordinated to both the methylated and the benzenic aromatic ring. A single-crystal X-ray diffraction measurement has been performed on the [(η⁶-5,6,7,8,9,10-C₁₁H₁₀)Cr(CO)₃] isomer, which presents the metal carbonyl moiety attached to the benzenic arene ligand. The products of reaction have been studied by UV–VIS–NIR, fluorescence and ¹H NMR spectroscopies. A detailed vibrational characterisation by mean of experimental FT-IR and Raman spectroscopy and DFT calculations is reported. The electron ligand donation to the metal carbonyl system, determined by FT-IR spectroscopy, has been related to the actual decrease of resonance energy of the aromatic hydrocarbon in the complex and compared with other chromium tricarbonyl complexes of different polycyclic aromatic hydrocarbons provided with the naphthalenic moiety.     

Structural characterization of electrodeposited copper hexacyanoferrate films by using a spectroscopic multi-technique approach

A deep structural investigation predominantly by X-ray spectroscopic techniques is conducted on films of copper hexacyanoferrate (CuHCF) deposited under different conditions, aimed at establishing structure-properties relationships. We show that the potentiodynamic electrosynthesis of CuHCF on carbon-based surfaces produces a highly disordered material, with a variable amount of Prussian Blue (PB). The subsequent Cu(2+) intercalation induces the partial conversion of PB into CuHCF, which explains the improved electrocatalytic properties after the intercalation process. Both Cu and Fe K-edge data have been recorded. For the sample with the lower amount of PB, we could perform a multiple edge data analysis to determine the local atomic environment around both metal centres using the same set of structural parameters. The presence of high multiplicity Cu-N-C-Fe linear chains has allowed us to determine accurately the local environment of Fe while fitting the Cu K-edge data only. Using this approach we have retrieved structural information around Fe for those samples in which the concomitant presence of PB would have made impossible the analysis of the Fe K-edge. The Fe-C, C-N and Cu-N bond distances have been found in agreement with those of the bulk structures, but higher values of [Fe(CN)(6)] vacancies for the building blocks have been evidenced, reaching a value of ~45% in one sample. XANES, Raman and SEM data agree with the model proposed for each studied electrode.     

Multi-frame pyramid correlation for time-resolved PIV

A novel technique is introduced to increase the precision and robustness of time-resolved particle image velocimetry (TR-PIV) measurements. The innovative element of the technique is the linear combination of the correlation signal computed at different separation time intervals. The domain of the correlation signal resulting from different temporal separations is matched via homothetic transformation prior to the averaging of the correlation maps. The resulting ensemble-averaged correlation function features a significantly higher signal-to-noise ratio and a more precise velocity estimation due to the evaluation of a larger particle image displacement. The method relies on a local optimization of the observation time between snapshots taking into account the local out-of-plane motion, continuum deformation due to in-plane velocity gradient and acceleration errors. The performance of the pyramid correlation algorithm is assessed on a synthetically generated image sequence reproducing a three-dimensional Batchelor vortex; experiments conducted in air and water flows are used to assess the performance on time-resolved PIV image sequences. The numerical assessment demonstrates the effectiveness of the pyramid correlation technique in reducing both random and bias errors by a factor 3 and one order of magnitude, respectively. The experimental assessment yields a significant increase of signal strength indicating enhanced measurement robustness. Moreover, the amplitude of noisy fluctuations is considerably attenuated and higher precision is obtained for the evaluation of time-resolved velocity and acceleration.     

Chemistry of the μ-hydridobis[pentacarbonylchromium(0)] Species. Part II. Acidification reaction of its derivatives with hydrogen chloride

Summary The Bu₄N[Cr₂H(CO)₁₀] species reacts with hydrogen chloride in methanol to produce Bu₄N[Cr(CO)₅Cl].Analogous reactions using the complex K(phen)₃Cr₂H(CO)₁₀ and K(bpy)₂Cr₂H(CO)₁₀ salts (phen = 1,10-phenanthroline, bpy = 2,2-bipyridine) give the new (phen)₂H[Cr₂H(CO)₁₀], phenH[Cr₂H(CO)₁₀], (phenH)₂(Cl)[Cr₂H(CO)₁₀], and bpyH[Cr₂H(CO)₁₀] derivatives respectively.     

Highly conductive Ni steam reforming catalysts prepared by electrodeposition

New highly conductive, active and stable Ni steam reforming catalysts were prepared through a method consisting of the calcination of a hydrotalcite-like compound electrodeposited in a single step on FeCrAlloy foams.