On the reduction of NiO forms in magnesia supported catalysts

Reducibility of Ni/MgO catalysts has been studied by the temperature-programmed reduction (TPR) technique in the temperature range of 373–1273 K. The profile of reduction reveals the presence of various forms of NiO. The effects of nickel loading and treatment temperature on catalyst reducibility have been evaluated. The formation of NiO–MgO solid solution controls the whole reduction of Ni/MgO system.

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Ni/MgO 373–1273 . NiO. . Ni/MgO NiO–MgO.

     

Low oxidation state ruthenium chemistry : IV. The reactions of M(CO)2(PPh3)3 complexes (M = Fe,Ru) and the hydrogenation and isomerization of alkenes catalyzed by RuL(CO)2(PPh3)2 (L = H2, PPh3)

The complexes M(CO)₂(PPh₃)₃ (I, M = Fe; II, M = Ru) readily react with H₂ at room temperature and atmospheric pressure to give cis-M(H)₂(CO)₂(PPh₃)₂ (III, M = Fe;IV,M = Ru). I reacts with O₂ to give an unstable compound in solution, in a type of reaction known to occur with II which leads to cis-Ru(O₂)(CO)₂(PPh₃)₂(V). Even compound IV reacts with O₂ to give V with displacement of H₂; this reaction has been shown to be reversible and this is the first case where the displacement of H₂ by O₂ and that of O₂ by H₂ at a metal center has been observed. III and IV are reduced to M(CO)₃(PPh₃)₂ by CO with displacement of H₂; Ru(CO)₃- (PPh₃)₂ is also formed by treatment of IV with CO₂, but under higher pressure. Compounds II and IV react with CH₂CHCN to give Ru(CH₂CHCN)(CO)₂- (PPh₃)₂(VI) which reacts with H₂ to reform the hydride IV.cis-Ru(H)₂(CO)₂(PPh₃)₂(IV) has been studied as catalyst in the hydrogenation and isomerization of a series of monoenes and dienes. The catalysts are poisoned by the presence of free triphenylphosphine. On the other hand the ready exchange of H₂ and O₂ on the “Ru(CO)₂(PPh₃)₂” moiety makes IV a catalyst not irreversibly poisoned by the presence of air. It has been found that even Ru(CO)₂(PPh₃)₃(II) acts as a catalyst for the isomerization of hex-1-ene at room temperature under an inert atmosphere.     

Cluster and periodic DFT calculations of MgO/Pd(CO) and MgO/Pd(CO)(2) surface complexes

The bonding and vibrational properties of Pd(CO) and Pd(CO)(2) complexes formed at the (100) surface of MgO have been investigated using the gradient-corrected DFT approach and have been compared to the results of infrared and thermal desorption experiments performed on ultrathin MgO films. Two complementary approaches have been used for the calculation of the electronic properties: the embedded cluster method using localized atomic orbital basis sets and supercell periodic calculations using plane waves. The results show that the two methods provide very similar answers, provided that sufficiently large supercells are used. Various regular and defect adsorption sites for the Pd(CO) and Pd(CO)(2) have been considered: terraces, steps, neutral and charged oxygen vacancies (F and F(+) centers), and divacancies. From the comparison of the computed and experimental results, it is concluded that the most likely site where the Pd atoms are stabilized and where carbonyl complexes are formed are the F(+) centers, paramagnetic defects consisting of a single electron trapped in an anion vacancy.     

Turbulence in microfluidics: Cleanroom-free,fast, solventless,and bondless fabrication and application in high throughput liquid-liquid extraction

This paper addresses an important breakthrough in the deployment of ultra-high adhesion strength microfluidic technologies to provide turbulence at harsh flow rate conditions. This paper is only, to our knowledge, the second reporting on the generation of high flow rate-assisted turbulence in microchannels. This flow solves a crucial bottleneck in microfluidics: the generation of high throughput homogeneous mixings. We focused on the fabrication of bulky polydimethylsiloxane (PDMS) microchips (without any interfaces) rather than the laborious surface modifications that were employed in the first reporting about turbulence-assisted microfluidics. The fabrication is cleanroom-free, simple, low-cost, fast, solventless, and bondless requiring only a laboratory oven. More specifically, our method relies on the shaping of a nylon scaffold, cure of PDMS with embedded nylon, and removal of this scaffold. The scaffold was obtained by manually wrapping nylon threads. The withdrawing out of the scaffold was completed in few seconds using only a plier. Such microchannels endured flow rates of up to 60.0 mL min⁻¹ with a strikingly low elastic deformation. The importance in producing turbulence into microscale channels was successfully shown in liquid-liquid extractions. The great energy dissipation rate relative to the turbulence created high throughput and efficient extractions in microfluidics for the first time. The residence time was only 0.01 s at 25.0 mL min⁻¹ (total flow rate of the immiscible phases). In addition, the partition coefficient determined in a single run was similar to that obtained by the conventional batch shake-flask method that was realized in triplicate.     

Metamagnetism

This is a review of the physical properties of metamagnets. These are antiferromagnets which, upon the application of a magnetic field, can undergo first-order magnetic phase transitions to a state with a relatively large magnetic moment. The treatments of mean field theory describing these materials are reviewed, as are the treatments of more modern theories. The experimental properties of the known metamagnets are discussed, with emphasis on the variety of means by which the metamagnetic transitions have been observed and studied. For some materials, there have been studies of the tricritical behaviour, and a discussion of the experimental results of these studies is given, along with a comparison of the results with the present theory.     

Multimetallic Oxynitrides Nanoparticles for a New Generation of Photocatalysts

A versatile synthetic strategy for the preparation of multimetallic oxynitrides has been designed and here exemplarily discussed considering the preparation of nanoscaled zinc–gallium oxynitrides and zinc–gallium–indium oxynitrides, two important photocatalysts of new generation, which proved to be active in key energy related processes from pollutant decomposition to overall water splitting. The synthesis presented here allows the preparation of small nanoparticles (less than 20 nm in average diameter), well-defined in size and shape, yet highly crystalline and with the highest surface area reported so far (up to 80 m² g⁻¹). X-ray diffraction studies show that the final material is not a mixture of single oxides but a distinctive compound. The photocatalytic properties of the oxynitrides have been tested towards the decomposition of an organic dye (as a model reaction for the decomposition of air pollutants), showing better photocatalytic performances than the corresponding pure phases (reaction constant 0.22 h⁻¹), whereas almost no reaction was observed in absence of catalyst or in the dark. The photocatalysts have been also tested for H₂ evolution (semi-reaction of the water splitting process) with results comparable to the best literature values but leaving room for further improvement.     

Ultra-stable microwave generation with a diode-pumped solid-state laser in the 1.5-μm range

We demonstrate the first ultra-stable microwave generation based on a 1.5-μm diode-pumped solid-state laser (DPSSL) frequency comb. Our system relies on optical-to-microwave frequency division from a planar-waveguide external cavity laser referenced to an ultra-stable Fabry–Perot cavity. The evaluation of the microwave signal at ~10 GHz uses the transportable ultra-low-instability signal source ULISS^®, which employs a cryo-cooled sapphire oscillator. With the DPSSL comb, we measured ?125 dBc/Hz phase noise at 1 kHz offset frequency, likely limited by the photo-detection shot-noise or by the noise floor of the reference cryo-cooled sapphire oscillator. For comparison, we also generated low-noise microwave using a commercial Er:fiber comb stabilized in similar conditions and observed >20 dB lower phase noise in the microwave generated from the DPSSL comb. Our results confirm the high potential of the DPSSL technology for low-noise comb applications.