A Theoretical study on the charge and discharge states of Na-ion battery cathode material,Na1+xFePO4F

Na₂FePO₄F is a promising cathode material for a Na-ion battery because of its high electronic capacity and good cycle performance. In this work, first principle calculations combined with cluster expansion and the Monte Carlo method have been applied to analyze the charge and discharge processes of Na₂FePO₄F by examining the voltage curve and the phase diagram. As a result of the density functional theory calculation and experimental verification with structural analysis, we found that the most stable structure of Na_1.5FePO₄F has the P2₁/b11 space group, which has not been reported to date. The estimated voltage curve has two clear plateaus caused by the two-phase structure composed of P2₁/b11 Na_1.5FePO₄F and Pbcn Na₂FePO₄F or Na₁FePO₄F and separated along the c-axis direction. The phase diagram shows the stability of the phase-separated structure. Considering that Na₂FePO₄F has diffusion paths in the a- and c-axis directions, Na₂FePO₄F has both innerphase and interphase diffusion paths. We suggest that the stable two-phase structure and the diffusion paths to both the innerphase and interphases are a key for the very clear plateau. We challenge to simulate a nonequilibrium state at high rate discharge with high temperature by introducing a coordinate-dependent chemical potential. The simulation shows agreement with the experimental discharge curve on the disappearance of the two plateaus. © 2018 Wiley Periodicals, Inc.     

On the electronic structure and hydrogen evolution reaction activity of platinum group metal-based high-entropy-alloy nanoparticles

We report the synthesis of high-entropy-alloy (HEA) nanoparticles (NPs) consisting of five platinum group metals (Ru, Rh, Pd, Ir and Pt) through a facile one-pot polyol process. We investigated the electronic structure of HEA NPs using hard X-ray photoelectron spectroscopy, which is the first direct observation of the electronic structure of HEA NPs. Significantly, the HEA NPs possessed a broad valence band spectrum without any obvious peaks. This implies that the HEA NPs have random atomic configurations leading to a variety of local electronic structures. We examined the hydrogen evolution reaction (HER) and observed a remarkably high HER activity on HEA NPs. At an overpotential of 25 mV, the turnover frequencies of HEA NPs were 9.5 and 7.8 times higher than those of a commercial Pt catalyst in 0.05 M H₂SO₄ and 1.0 M KOH electrolytes, respectively. Moreover, the HEA NPs showed almost no loss during a cycling test and were much more stable than the commercial Pt catalyst. Our findings on HEA NPs may provide a new paradigm for the design of catalysts.

RuRhPdIrPt high-entropy-alloy nanoparticles with a broad and featureless valence band spectrum show high hydrogen evolution reaction activity.     

Direct Introduction of a Dimesitylboryl Group Using Base‐Mediated Substitution of Aryl Halides with Silyldimesitylborane

The first dimesitylboryl substitution of aryl halides with a silylborane bearing a dimesitylboryl group in the presence of alkali‐metal alkoxides is described. The reactions of aryl bromides or iodides with Ph₂MeSi?BMes₂ and Na(OtBu) afforded the desired aryl dimesitylboranes in good to high yields and with high borylation/silylation ratios. Selective reaction of the sterically less‐hindered C?Br bond of dibromoarenes provided monoborylated products. This reaction was used to rapidly construct a D‐π‐A aryl dimesityl borane with a non‐symmetrical biphenyl spacer.     

Synthesis of a Pentacene‐Type Silaborin via Double Dehydrogenative Cyclization of 1,4‐Diboryl‐2,5‐disilylbenzene

A new pentacene‐type silaborin, in which three benzene rings are bridged by silicon and boron atoms, has been synthesized and characterized by using NMR spectroscopy and X‐ray crystallographic analysis. The precursor, 1,4‐bis(dimesitylboryl)‐2,5‐bis(phenylsilyl)benzene ( 4 ), was prepared by stepwise introduction of a silyl group and a boryl group to a benzene ring starting from 1,4‐dibromobenzene. Double cyclization of 4 proceeds by a H‐Mes exchange and a B‐H/C‐H dehydrogenative condensation to afford pentacene‐type silaborin 5 . X‐ray crystal structure analysis reveals that 5 adopts a bent structure rather than a planar one. UV/Vis spectra and DFT calculations for 5 reveal a lowering of the LUMO energy level compared with corresponding anthracene‐type 3 .     

Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (d_Au) at 5.3 nm≤d_Au≤8.2 nm. Light irradiation (λ_ex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.     

Biohybrid Organic Heterostructure Based on Chlorophyll-Bacteriochlorophyll Aggregates for Ecofriendly Hydrogen Production

Hydrogen energy is an abundant, clean, sustainable and environmentally friendly renewable energy source. Therefore, the production of hydrogen by photocatalytically splitting water on semiconductors has been considered in recent years as a promising and sustainable strategy for converting solar energy into chemical energy to replace conventional energy sources and to solve the growing problem of environmental pollution and the global energy crisis. However, highly efficient solar-driven photocatalytic hydrogen production remains a huge challenge due to the poor visible light response of available photocatalytic materials and the low efficiency of separation and transfer of photogenerated electron-hole pairs. In the present work, organic heterojunction structures based on bacteriochlorophyll (BChl) and chlorophyll (Chl) molecules were introduced and used for solar-driven photocatalytic hydrogen production from water under visible light. Also, noble metal-free photocatalyst was successfully constructed on Ti₃C₂T_x nanosheets by simple successive deposition of Chl and BChl, which was used for the photocatalytic splitting water to hydrogen evolution reaction (HER). The results show that the optimal BChl@Chl@Ti₃C₂T_x composite has a high HER performance with 114 μmol/h/g_cat, which is much higher than the BChl@Ti₃C₂T_x and Chl@Ti₃C₂T_x composites.     

Interaction of highly charged ions with carbon-based materials using Kobe EBIS

Interaction of highly charged ions (HCIs) with surfaces produce various specific phenomena as a consequence of the potential energy that HCI possesses. In the present study, we have observed photon emission, structural, magnetic, and electronic modification on various carbon-based materials such as carbon nanotube by the impact of HCIs using an electron beam ion source named Kobe EBIS installed at the Kobe University. In order to study the potential effect, HCIs of Ar^q+ (q = 6–16) with the intensity of 0.1–1 nA are projected on the surface with a constant kinetic energy (16 keV). For photon emission measurements, we observed spatial and spectral distribution of visible light emission from the surface during irradiation with HCIs. On the other hand, the structural modification of multi-walled carbon nanotubes (MWCNTs) irradiated with HCIs has been analyzed using a transmission electron microscopy and Raman spectroscopy. Irradiation effects on the resistivity of single MWCNT supported on micrometer scale bridge pattern were also measured. We have also measured magnetic structure of highly oriented pyrolytic graphite irradiated with HCIs using electron spin resonance at low temperature. At the present paper, we will review our recent experimental results on the interaction of HCI with various carbon-based materials.     

Molecular Insights into the Ligand-Based Six-Proton- and Six-Electron-Transfer Processes Between Tris-ortho-Phenylenediamines and Tris-ortho-Benzoquinodiimines

The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H₂) important. A high-spin (hs) Fe^II complex with o-phenylenediamine (opda) ligands, [Fe^II(opda)₃]²⁺ (hs- [6R] ²⁺), was reported showing photochemical H₂ evolution. In addition, a low-spin (ls) [Fe^II(bqdi)₃]²⁺ (bqdi: o-benzoquinodiimine) (ls- [0R] ²⁺) formation by O₂ oxidation of hs- [6R] ²⁺, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls- [0R] [PF₆]₂ can be reduced by hydrazine giving ls-[Fe^II(opda)(bqdi)₂][PF₆]₂ (ls- [2R] [PF₆]₂) and ls-[Fe^II(opda)₂(bqdi)][PF₆]₂ (ls- [4R] [PF₆]₂) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials.