Core‐Shell Structured Cobalt Sulfide/Cobalt Aluminum Hydroxide Nanosheet Arrays for Pseudocapacitor Application

The direct synthesis of nanostructured electrode materials on three‐dimensional substrates is important for their practical application in electrochemical cells without requiring the use of organic additives or binders. In this study, we present a simple two‐step process to synthesize a stable core–shell structured cobalt sulfide/cobalt aluminum hydroxide nanosheet (LDH‐S) for pseudocapacitor electrode application. The cobalt aluminum layered double hydroxide (CoAl‐LDH) nanoplates were synthesized in basic aqueous solution with a kinetically‐controlled thickness. Owing to the facile diffusion of electrolytes through the nanoplates, thin CoAl‐LDH nanoplates have higher specific capacitance values than thick nanoplates. The as‐grown CoAl‐LDH nanoplates were transformed into core–shell structured LDH‐S nanosheets by a surface modification process in Na₂S aqueous solution. The chemically robust cobalt sulfide (CoS) shell increased the electrochemical stability compared to the sulfide‐free CoAl‐LDH electrodes. The LDH‐S electrodes exhibited high electrochemical performance in terms of specific capacitance and rate capability with a galvanostatic discharge of 1503 F g^?1 at a current density of 2 A g^?1 and a specific capacitance of 91 % at 50 A g^?1.     

Ligand Hybridization for Electro-reforming Waste Glycerol into Isolable Oxalate and Hydrogen

The electro-reforming of glycerol is an emerging technology of simultaneous hydrogen production and biomass valorization. However, its complex reaction network and limited catalyst tunability restrict the precise steering toward high selectivity. Herein, we incorporated the chelating phenanthrolines into the bulk nickel hydroxide and tuned the electronic properties by installing functional groups, yielding tunable selectivity toward formate (max 92.7 %) and oxalate (max 45.3 %) with almost linear correlation with the Hammett parameters. Further combinatory study of intermediate analysis and various spectroscopic techniques revealed the electronic effect of tailoring the valence band that balances between C−C cleavage and oxidation through the key glycolaldehyde intermediate. A two-electrode electro-reforming setup using the 5-nitro-1,10-phenanthroline-nickel hydroxide catalyst was further established to convert crude glycerol into pure H₂ and isolable sodium oxalate with high efficiency.     

Unravelling the Complex LiOH-Based Cathode Chemistry in Lithium–Oxygen Batteries**

The LiOH-based cathode chemistry has demonstrated potential for high-energy Li−O₂ batteries. However, the understanding of such complex chemistry remains incomplete. Herein, we use the combined experimental methods with ab initio calculations to study LiOH chemistry. We provide a unified reaction mechanism for LiOH formation during discharge via net 4 e⁻ oxygen reduction, in which Li₂O₂ acts as intermediate in low water-content electrolyte but LiHO₂ as intermediate in high water-content electrolyte. Besides, LiOH decomposes via 1 e⁻ oxidation during charge, generating surface-reactive hydroxyl species that degrade organic electrolytes and generate protons. These protons lead to early removal of LiOH, followed by a new high-potential charge plateau (1 e⁻ water oxidation). At following cycles, these accumulated protons lead to a new high-potential discharge plateau, corresponding to water formation. Our findings shed light on understanding of 4 e⁻ cathode chemistries in metal–air batteries.     

Electropolymerization rates of polythiophene/polypyrrole composite polymer with some dopant ions

Pyrrole, thiophene, and a mixture of the two monomers were electrochemically polymerized to investigate polymerization rates and the morphology change of the polymer matrix, and to improve the aging and cyclic voltammetric behaviors of the polymers. Thiophene was polymerized on a smooth surface of Pt electrode by two steps. The first step was controlled by electron transfer at the electrical double layer and the other by diffusion of the monomer reacting on the immobilized layer consisting of the precoated thiophene polymer. The electropolymerization rate of the second step was 1.85 × 10⁻⁴ cm³ mol⁻¹ s⁻¹, which is faster by 8.63 × 10² times than the first step. Some supporting electrolytes such as KPF₆, LiClO₄, TBAP, and TBABF₄ were employed in the polymerization reaction to see the effects of dopant anions on the polymerization rate, and KPF₆ was the fastest one at 2.41 × 10⁻⁶ cm s⁻¹. However, owing to its sensitivity to oxygen, LiClO₄ was used for the polymerization that is fairly stable in air and the same rate as KPF₆. For the competitive polymerization reaction of the two monomers the rate of thiophene was found to be about 11 times slower than that of thiophene alone. When the starting concentration of the thiophene monomer was higher than pyrrole by five times, its portion in the composite polymer was found to be only 8–10%. However, this level gave desirable results in terms of redox properties and aging. The resistance against aging was explained by the morphology change, which came from great shrinking of its porosity. © 1997 John Wiley & Sons, Inc.     

Determination of Erbium by Two-Color Three-Photon Resonance Ionization Mass Spectrometry

Excited states and autoionization states of the erbium atom were investigated by the use of multicolor resonance ionization mass spectrometry. Among the observed first excited states, a level [4f¹²(³H₆)6s6p(³P₁)] located 17,348 cm⁻¹from the ground state is regarded as the most efficient state for excitation within the wavelength range investigated (560–600 nm), while a level located 17,080 cm⁻¹from this first excited state (E= 34,458 cm⁻¹) is identified as the best second excited state for the optimal photoionization scheme. Many ionization schemes adopting an autoionization state are also investigated, and the most efficient scheme is identified as 4f¹²6s²(³H₆) → 4f¹²(³H₆)6s6p(³P₁⁰), 17,348 cm⁻¹→ 34,458 cm⁻¹→ continuum state, which corresponds to the two-color (ω₁+ ω₂+ ω_1,2) scheme. Various concentrations of standard solutions for erbium are determined and the minimum amount detectable by two-color three-photon ionization was determined to be 20 pg.     

Metabolic mechanisms of a drug revealed by distortion-free 13C tracer analysis

Metabolomic isotopic tracing can provide flux information useful for understanding drug mechanisms. For that, NMR has the unique advantage of giving positional isotope enrichment information, but the current ¹³C 1D NMR approach suffers from low sensitivity and high overlaps. We developed a new 2D heteronuclear NMR experiment incorporating J-scaling and distortion-free elements that allows for quantitative analysis of multiplets with high sensitivity and resolution. When applied to an old chemotherapeutic drug, the approach provided a quantitative estimation of TCA-cycle turns, confirming the conventional mechanism of its mitochondrial metabolic enhancement. Additionally, the approach identified a new mechanism of the higher contribution of the pentose phosphate pathway to serine synthesis in the cytosolic compartment, possibly explaining the broad pharmacological activities of the drug. Our approach may prove beneficial in helping to find new usages or metabolic mechanisms of other drugs.

Our approach provides high-resolution and distortion-free NMR for metabolic tracer analysis. It confirmed the conventional mechanism of dichloroacetate and suggested a new one involving an enhanced contribution of PPP to cytosolic serine synthesis.