To clarify the origin of the polarization of magnesium deposition/dissolution reactions, we combined electrochemical measurement, operando soft X-ray absorption spectroscopy (operando SXAS), Raman, and density functional theory (DFT) techniques to three different electrolytes: magnesium bis­(trifluoromethanesulfonyl)­amide (Mg­(TFSA)2)/triglyme, magnesium borohydride (Mg­(BH4)2)/tetrahydrofuran (THF), and Mg­(TFSA)2/2-methyltetrahydrofuran (2-MeTHF). Cyclic voltammetry revealed that magnesium deposition/dissolution reactions occur in Mg­(TFSA)2/triglyme and Mg­(BH4)2/THF, while the reactions do not occur in Mg­(TFSA)2/2-MeTHF. Raman spectroscopy shows that the [TFSA]− in the Mg­(TFSA)2/triglyme electrolyte largely does not coordinate to the magnesium ions, while all of the [TFSA]− in Mg­(TFSA)2/2-MeTHF and [BH4]− in Mg­(BH4)2/THF coordinate to the magnesium ions. In operando SXAS measurements, the intermediate, such as the Mg+ ion, was not observed at potentials above the magnesium deposition potential, and the local structure distortion around the magnesium ions increases in all of the electrolytes at the magnesium electrode|electrolyte interface during the cathodic polarization. Our DFT calculation and X-ray photoelectron spectroscopy results indicate that the [TFSA]−, strongly bound to the magnesium ion in the Mg­(TFSA)2/2-MeTHF electrolyte, undergoes reduction decomposition easily, instead of deposition of magnesium metal, which makes the electrolyte inactive electrochemically. In the Mg­(BH4)2/THF electrolyte, because the [BH4]− coordinated to the magnesium ions is stable even under the potential of the magnesium deposition, the magnesium deposition is not inhibited by the decomposition of [BH4]−. Conversely, because [TFSA]− is weakly bound to the magnesium ion in Mg­(TFSA)2/triglyme, the reduction decomposition occurs relatively slowly, which allows the magnesium deposition in the electrolyte.

Fluoride ion batteries (FIBs) are regarded as promising energy storage devices, and it is important and urgent to develop cathode materials with high energy densities for use in FIBs.

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The Z-scheme CO2 reduction activity of metal complex–semiconductor hybrid photocatalysts was investigated in detail with a focus on the interfacial electron transfer process. Semiconductors of GaN:ZnO solid solutions, TaON, and Ta/N-codoped TiO2 were examined as components of the hybrid photocatalyst in combination with a binuclear Ru­(II) complex. The (photo)­physical properties of the semiconductor part were found to strongly affect the efficiency of interfacial electron transfer from/to the Ru complex photosensitizer unit, which was attached to the semiconductor surface. The photocatalytic activity of the hybrids showed a reasonable relationship with the efficiencies of forward and backward electron transfer. Among the three semiconductors, the highest activity was obtained with GaN:ZnO, which had the most negative conduction band potential among the semiconductors examined. The experimental results clearly demonstrated that analyses of the emission quenching process of the excited photosensitizer moiety of the binuclear Ru­(II) complex allowed visualization of the interfacial electron transfer between the semiconductor and the Ru complex, giving us a rational guideline to improve the efficiency of the hybrid photocatalyst for Z-scheme CO2 reduction.

The prevalence of nonsyndromic cleft lip with or without cleft palate (CL/P) and cleft palate only (CPO) are believed to be higher in the Japanese than in Americans, Europeans or Africans. The purpose of this study was to investigate, in a Japanese population, relationships between CL/P or CPO and seven candidate genes (TGFB3, DLX3, PAX9, CLPTM1, TBX10, PVRL1, TBX22) that showed positive associations in other populations and are expressed in the oral/lip region in developing mice. We first searched for mutations in these genes among 112 CL/P and 16 CPO patients, and found a heterozygous missense mutation (640A>G, S214G) in exon 3 of PAX9 in two sibs with CL/P and their phenotypically normal mother from a Japanese family. A population-based case-control analysis and a familybased transmission disequilibrium test (TDT), using single nucleotide polymorphisms (SNPs), and two-SNP haplotypes of the genes, between the 112 CL/P cases with their parents and 192 controls indicated a significant association at one SNP site, IVS1+5321, in TGFB3 with a P-value of 0.0016. Population-based haplotyping revealed that the association was most significant for haplotype ''A/A'' consisting of IVS1+5321 and IVS1À1572; TDT also gave a P-value of 0.0252 in this haplotype.

and sustainable society; however, LIBs are facing bottlenecks in terms of energy/ power density and safety. [1,2] In recent decades, many new concepts for batteries have been proposed as potential alternatives for LIBs, such as battery systems that employ Na + , K + , Mg 2+ , Zn 2+ , Ca 2+ , Al 3+ , F − , or Cl − as charge carriers, which have significantly expanded the strategies for developing next-generation batteries with high energy and power densities. [3,4] All-solid-state fluoride-ion batteries (FIBs) have received widespread attention because of the high electronegativity of fluorine. This leads to extraordinary anodic electrochemical stability, resulting in superior reliability for solid-state utilization. In early studies, including our recent ones, simple metal/metal fluoride (M/MF x ) systems were first used as electrode materials with high theoretical capacities. [3,[5][6][7][8][9] Using M/MF x systems, it is theoretically feasible to fabricate batteries with high energy densities because the working potential can exceed 3 V if suitable cathode-anode combinations are selected. However, closepacked metal atoms (e.g., Cu, Co, Ni, and Bi) provide no diffusion path for F anions in conversion-type M/MF x systems; as a result, M/MF x systems inevitably suffer from thorough atomic rearrangements and undesired volumetric changes upon All-solid-state fluoride-ion batteries (FIBs) are regarded as promising energy storage devices; however, currently proposed cathodes fail to meet the requirements for practical applications in terms of high energy density and high rate capability. Herein, the first use of stable and low-cost cuprous oxide (Cu 2 O) as a cathode material for all-solid-state FIBs with reversible and fast (de)fluorination behavior is reported. A phase-transition reaction mechanism involving Cu + /Cu 2+ redox for charge compensation is confirmed, using the combination of electrochemical methods and X-ray absorption spectroscopy. The first discharge capacity is approximately 220 mAh g −1 , and fast capacity fading is observed in the first five cycles, which is ascribed to partial structural amorphization. Compared with those of simple metal/metal fluoride systems, the material shows a superior rate capability, with a first discharge capacity of 110 mAh g −1 at 1 C. The rate-determining step and probable structural evolutions are investigated as well. It is believed that the comprehensive investigations of Cu 2 O as a cathode material described in this work can lead to an improved understanding of all-solid-state FIBs.

All-solid-state lithium batteries that use lithium metal as the anode have extremely high energy densities. However, for lithium metal anodes to be used, lithium dendrite formation must be addressed. Recently, the addition of lithium iodide (LiI) to sulfide solid electrolytes was found to suppress lithium dendrite formation. It is unclear whether the cause of this suppression is the improvement of the ionic conductivity of the solid electrolyte itself or the electrochemical properties of the lithium metal/solid electrolyte interface. In this study, the cause of the suppression was quantitatively elucidated. The effect of the interphase on the dendrite growth of doping LiI into Li3PS4 was determined using X-ray absorption spectroscopy and X-ray computed tomography measurements. The results revealed that LiI-doped Li3PS4 suppressed the dendrite formation by maintaining the interface due to inhibition of the reductive decomposition of Li3PS4. In addition, annealed LiI-doped Li3PS4 showed a greater dendrite suppression ability as the ionic conductivity increased. From these results, we not only found that the physical properties of the lithium metal/solid electrolyte interface and the bulk ionic conductivity contribute to lithium dendrite suppression but also quantitatively determined the proportions of the contributions of these two factors.