Laser-induced breakdown spectroscopy to obtain quantitative three-dimensional hydrogen mapping in a nickel-metal-hydride battery cathode for interpreting its reaction distribution.

We present a method for obtaining a three-dimensional quantitative hydrogen distribution in a Ni-MH battery cathode using laser-induced breakdown spectroscopy (LIBS) and demonstrate that the reaction distribution in the cathode can be interpreted based on a state-of-charge (SOC) distribution converted from the hydrogen distribution. In this method, we measured the hydrogen emission-line intensities at 656.28 nm for a model cathode cycled five times at 2.3 mA cm-2 and a commercial Ni-MH battery cathode cycled 1000 times at 1C under a 3000 Pa helium atmosphere. Our results show that the average SOC in the SOC distributions of the cathodes agreed with those evaluated from X-ray diffraction and charge-discharge curves and that the overcharged areas exhibited SOC values above 100%. The present LIBS method will allow us to understand the deterioration mechanism of a Ni-MH battery and improve its cycle life and capacity.

Quantitative Analysis of Hydrogen in High-Hydrogen-Content Material of Magnesium Hydride via Laser-Induced Breakdown Spectroscopy.

An analytical approach that can rapidly determine a wide range of hydrogen concentration in solid-state materials has been recently demanded to contribute to the hydrogen economy. This study presents a method for estimating hydrogen concentrations ranging from 0.2 to 7.6 mass % via laser-induced breakdown spectroscopy (LIBS) in a few seconds, with an improvement in the upper limit of determination (7.6 mass %) by approximately 1.3 times compared with a previous work (5.7 mass %). This extension of the determinable concentration range was achieved by measuring the emission intensity at 656.28 nm from the sample in a helium atmosphere at 3000 Pa under focused laser irradiation and by reducing the water residues in both the sample and gas line of the LIBS system. The as-determined hydrogen concentrations in magnesium hydride (MgH2) samples agreed well with those estimated through inert gas fusion/gas chromatography. The calibration curve for LIBS analysis was acquired by measuring the emission intensity at 656.28 nm of standard Mg/MgH2 mixtures containing various hydrogen concentrations (0, 0.1, 0.2, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, and 7.6 mass %). Results indicated that the proposed LIBS-based method is applicable to the rapid quantitative analysis of hydrogen in hydrogen-containing material of MgH2.

Chiral Bicyclic NHC/Cu Complexes for Catalytic Asymmetric Borylation of α,ß-Unsaturated Esters.

The potential of using chiral bicyclic NHC ligands that exhibit modularity was investigated in the Cu-catalyzed asymmetric borylation reaction of α,ß-unsaturated esters. After screening for ligands and optimization of the reaction conditions, the corresponding products were afforded with good enantioselectivities (up to 85% ee).

Chiral bicyclic NHC/Ir complexes for catalytic asymmetric transfer hydrogenation of ketones.

A diverse series of chiral bicyclic NHC/Ir complexes were prepared via a previously developed divergent synthesis of chiral imidazolium salts. Among the complexes, 8dz was found to be an excellent catalyst precursor for the Ir-catalyzed asymmetric transfer hydrogenation of ketones. The reaction of ketones with 8dz proceeded smoothly to give corresponding alcohols with high enantioselectivities (up to 98%) and productivities (TON up to 4500).

Enantioselective synthesis of planar-chiral ferrocene-fused 4-pyridones and their application in construction of pyridine-based organocatalyst library.

A couple of planar-chiral ferrocene-fused 4-pyridone derivatives 2a and 2b were synthesized in enantiomerically pure form by scalable asymmetric transformations. Pyridones 2 are versatile precursors to various ferrocene-fused pyridine derivatives, which are useful nucleophilic asymmetric organocatalysts.