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Unprecedented selective homogeneous cobalt-catalysed reductive alkoxylation of cyclic imides under mild conditions
The first general and efficient non-noble metal-catalysed reductive C2-alkoxylation of cyclic imides (phthalimides and succinimides) is presented. Crucial for the success is the use of [Co(BF4)2·6H2O/triphos (L1)] combination and no external additives are required. Using the optimal cobalt-system, the hydrogenation of the aromatic ring of the parent phthalimide is avoided and only one of the carbonyl groups is selectively functionalized. The resulting products, N- and aryl-ring substituted 3-alkoxy-2,3-dihydro-1H-isoindolin-1-one and N-substituted 3-alkoxy-pyrrolidin-2-one derivatives, are prepared under mild conditions in good to excellent isolated yields. Intramolecular reductive couplings can also be performed affording tricyclic compounds in a one-step process. The present protocol opens the way to the development of new base-metal processes for the straightforward synthesis of functionalized N-heterocyclic compounds of pharmaceutical and biological interest.
Temperature-dependent electric noise level in different iron-based superconductors
The magnetic flux penetration into the melt-textured Y-Ba-Cu-O high temperature superconducting bulk magnets were precisely evaluated during and after the pulsed field magnetization processes operated at 30 K. The bulk magnets were carefully fabricated by the cold seeding method with use of a single and a pair of seed crystals composed of the Nd-Ba-Cu-O thin films. These seed crystals were put on the top surfaces of the precursors to let the large grains grow during the heat treatments. We observed the flux penetrations which occurred in the lower applied-field regions at around 3.1 T for the samples bearing the twin seeds than those of the single-seeded crystals at around 3.8 T. This means that the magnetic fluxes are capable of invading into the twin-seeded samples more easily than the single-seeds. It suggests that the anisotropic grain growths of parallel and normal to the rows of seed crystals affects the variations of Jc values with different distributions of the pinning centers, results in the preferential paths for the invading magnetic fluxes.
High-defect hydrophilic carbon cuboids anchored with Co/CoO nanoparticles as highly efficient and ultra-stable lithium-ion battery anodes
We propose an effective strategy to engineer a unique kind of porous carbon cuboid with tightly anchored cobalt/cobalt oxide nanoparticles (PCC–CoOx) that exhibit outstanding electrochemical performance for many key aspects of lithium-ion battery electrodes. The host carbon cuboid features an ultra-polar surface reflected by its high hydrophilicity and rich surface defects due to high heteroatom doping (N-/O-doping both higher than 10 atom%) as well as hierarchical pore systems. We loaded the porous carbon cuboid with cobalt/cobalt oxide nanoparticles through an impregnation process followed by calcination treatment. The resulting PCC–CoOx anode exhibits superior rate capability (195 mA h g−1 at 20 A g−1) and excellent cycling stability (580 mA h g−1 after 2000 cycles at 1 A g−1 with only 0.0067% capacity loss per cycle). Impressively, even after an ultra-long cycle life exceeding 10 000 cycles at 5 A g−1, the battery can recover to 1050 mA h g−1 at 0.1 A g−1, perhaps the best performance demonstrated so far for lithium storage in cobalt oxide-based electrodes. This study provides a new perspective to engineer long-life, high-power metal oxide-based electrodes for lithium-ion batteries through controlling the surface chemistry of carbon host materials.
Air-Stable CpCoI–Phosphite–Fumarate Precatalyst in Cyclization Reactions: Comparing Different Methods of Energy Supply
The robust CoI precatalyst [CpCo(P{OEt}3)(trans-MeO2CHC=CHCO2Me)] was investigated in cyclotrimerizations, furnishing benzenes and pyridines from triynes, diynes and nitriles, comparing the influence of different ways of energy supply; namely, irradiation and conventional (thermal) or microwave heating. The precatalyst was found to work under all conditions, including the possibility to catalyze cyclotrimerizations at room temperature under photochemical conditions at longer reaction times. Performance of the reactions in a microwave reactor proved to be the most time-efficient way to rapidly assemble the expected reaction products; however, careful selection of reaction conditions can be required. The synthesis of pyridines and isoquinolines successfully involved the utilization of versatile functionalized nitriles, affording structurally interesting reaction products. Comparison with the known and often applied precatalyst CpCo(CO)2 demonstrated the significantly higher reactivity of the CpCoI–phosphite–olefin precatalyst.
Cobalt-based nanoparticles prepared from MOF-carbon templates as efficient hydrogenation catalysts
The development of efficient and selective nanostructured catalysts for industrially relevant hydrogenation reactions continues to be an actual goal of chemical research. In particular, the hydrogenation of nitriles and nitroarenes is of importance for the production of primary amines, which constitute essential feedstocks and key intermediates for advanced chemicals, life science molecules and materials. Herein, we report the preparation of graphene shell encapsulated Co3O4- and Co-nanoparticles supported on carbon by the template synthesis of cobalt-terephthalic acid MOF on carbon and subsequent pyrolysis. The resulting nanoparticles create stable and reusable catalysts for selective hydrogenation of functionalized and structurally diverse aromatic, heterocyclic and aliphatic nitriles, and as well as nitro compounds to primary amines (>65 examples). The synthetic and practical utility of this novel non-noble metal-based hydrogenation protocol is demonstrated by upscaling several reactions to multigram-scale and recycling of the catalyst.
Femtosecond spectroscopy in a nearly optimally doped Fe-based superconductors FeSe0.5Te0.5 and Ba(Fe 1-xCox)2As2/Fe thin film
Femtosecond spectroscopy has been used to investigate the quasi-particle relaxation times in nearly optimally doped Fe-based superconductors FeSe 0.5Te0.5 and optimally doped Ba-122 thin films growth on a Fe buffer layer. Experimental results concerning the temperature dependence of the relaxation time of such pnictides both in the superconducting state are now presented and discussed. Modelling the T-dependence of relaxation times an estimation of both electron-phonon constant and superconducting energy gap in the excitation spectrum of both Fe(Se,Te) and Ba-122 compounds is obtained.
In situ single-shot diffractive fluence mapping for X-ray free-electron laser pulses
Free-electron lasers (FELs) in the extreme ultraviolet (XUV) and X-ray regime opened up the possibility for experiments at high power densities, in particular allowing for fluence-dependent absorption and scattering experiments to reveal non-linear light-matter interactions at ever shorter wavelengths. Findings of such non-linear effects are met with tremendous interest, but prove difficult to understand and model due to the inherent shot-to-shot fluctuations in photon intensity and the often structured, non-Gaussian spatial intensity profile of a focused FEL beam. Presently, the focused beam is characterized and optimized separately from the actual experiment. Here, we present the simultaneous measurement of XUV diffraction signals from solid samples in tandem with the corresponding single-shot spatial fluence distribution on the actual sample. Our in situ characterization scheme enables direct monitoring of the sample illumination, providing a basis to optimize and quantitatively understand FEL experiments.
Bicrystalline grain boundary junctions of Co-doped and P-doped Ba-122 thin films
We prepared GB junctions of Ba(Fe0.9Co0.1)2As2 thin films on bicrystalline [00 l]-tilt SrTiO3 substrates. The junctions show clear Josephson effects. Electrical characterization shows asymmetric I-V characteristics which can be described within the resistively shunted junction (RSJ) model. A large excess current is observed. Their formal ICRN product is 20.2 μV at 4.2 K, which is decreased to 6.5 μV when taking Iex into account. Fabrication methods to increase this value are discussed. Additionally, measurements on GB junctions of BaFe2(As0.66P0.34)2 thin films on LSAT bicrystalline substrates are shown. Their symmetric RSJ/flux flow-behavior exhibits a formal ICRN product of 45 μV, whereas the excess corrected value is ll μV.
Selective cobalt nanoparticles for catalytic transfer hydrogenation of N-heteroarenes
Nitrogen modified cobalt catalysts supported on carbon were prepared by pyrolysis of the mixture generated from cobalt(ii) acetate in aqueous solution of melamine or waste melamine resins, which are widely used as industrial polymers. The obtained nanostructured materials catalyze the transfer hydrogenation of N-heteroarenes with formic acid in the absence of base. The optimal Co/Melamine-2@C-700 catalyst exhibits high activity and selectivity for the dehydrogenation of formic acid into molecular hydrogen and carbon dioxide and allows for the reduction of diverse N-heteroarenes including substrates featuring sensitive functional groups.
Cobalt as a promising dopant for producing semi-insulating β -Ga2O3crystals: Charge state transition levels from experiment and theory
Optical absorption and photoconductivity measurements of Co-doped β-Ga2O3 crystals reveal the photon energies of optically excited charge transfer between the Co related deep levels and the conduction or valence band. The corresponding photoionization cross sections are fitted by a phenomenological model considering electron-phonon coupling. The obtained fitting parameters: thermal ionization (zero-phonon transition) energy, Franck-Condon shift, and effective phonon energy are compared with corresponding values predicted by first principle calculations based on density functional theory. A (+/0) donor level ∼0.85 eV above the valence band maximum and a (0/-) acceptor level ∼2.1 eV below the conduction band minimum are consistently derived. Temperature-dependent electrical resistivity measurement at elevated temperatures (up to 1000 K) yields a thermal activation energy of 2.1 ± 0.1 eV, consistent with the position of the Co acceptor level. Furthermore, the results show that Co doping is promising for producing semi-insulating β-Ga2O3 crystals.