Nutritional Value, Volatile Components, Functional Metabolites, and Antibacterial and Cytotoxic Activities of Different Parts of Millettia speciosa Champ., a Medicinal and Edible Plant with Potential for Development.

Highly nutritious traditional plants which are rich in bioactive substances are attracting increasing attention. In this study, the nutritional value, chemical composition, biological activities, and feed indices of different parts of Millettia speciosa were comprehensively evaluated. In terms of its nutritional value, this study demonstrated that the leaves, flowers and seeds of M. speciosa were rich in elements and amino acids; the biological values (BVs) of these ingredients ranged from 85% to 100%, showing the extremely high nutritional value of this plant. GC-MS analysis suggested that the main chemical components of the flower volatile oil were n-hexadecanoic acid (21.73%), tetracosane (19.96%), and pentacosane (5.86%). The antibacterial activities of the flower and seed extracts were significantly stronger than those of the leaves and branches. The leaf extract displayed the strongest antifungal activities (EC50 values: 18.28 ± 0.54 µg/mL for Pseudocryphonectria elaeocarpicola and 568.21 ± 33.60 µg/mL for Colletotrichum gloeosporioides) and were the least toxic to mouse fibroblasts (L929) (IC50 value: 0.71 ± 0.04 mg/mL), while flowers were the most toxic (IC50 value: 0.27 ± 0.03 mg/mL). In addition, the abundance of fiber, protein, mineral elements, and functional metabolite contents indicated the potential applicability of M. speciosa as an animal feed. In conclusion, as a traditional herbal plant used for medicinal and food purposes, M. speciosa shows potential for safe and multifunctional development.

Palladium-Phosphide-Modified Three-Dimensional Phospho-Doped Graphene Materials for Hydrogen Storage.

The development of efficient hydrogen storage materials is crucial for advancing hydrogen-based energy systems. In this study, we prepared a highly innovative palladium-phosphide-modified P-doped graphene hydrogen storage material with a three-dimensional configuration (3D Pd3P0.95/P-rGO) using a hydrothermal method followed by calcination. This 3D network hindering the stacking of graphene sheets provided channels for hydrogen diffusion to improve the hydrogen adsorption kinetics. Importantly, the construction of the three-dimensional palladium-phosphide-modified P-doped graphene hydrogen storage material improved the hydrogen absorption kinetics and mass transfer process. Furthermore, while acknowledging the limitations of primitive graphene as a medium in hydrogen storage, this study addressed the need for improved graphene-based materials and highlighted the significance of our research in exploring three-dimensional configurations. The hydrogen absorption rate of the material increased obviously in the first 2 h compared with two-dimensional sheets of Pd3P/P-rGO. Meanwhile, the corresponding 3D Pd3P0.95/P-rGO-500 sample, which was calcinated at 500 °C, achieved the optimal hydrogen storage capacity of 3.79 wt% at 298 K/4 MPa. According to molecular dynamics, the structure was thermodynamically stable, and the calculated adsorption energy of a single H2 molecule was -0.59 eV/H2, which was in the ideal range of hydrogen ad/desorption. These findings pave the way for the development of efficient hydrogen storage systems and advance the progress of hydrogen-based energy technologies.

Dissolution Mechanism of Eutectic and Hypereutectic Mg-Sn Alloy Anodes for Magnesium Rechargeable Batteries.

Magnesium rechargeable batteries (MRBs) are presently attracting much attention due to their low cost, high safety, and high theoretical volumetric capacity. Traditionally, pure magnesium metal has been used as an anode for MRBs, but its poor cycle performance, modest compatibility with conventional electrolytes, and sluggish kinetics limit the further development of MRBs. In this work, eutectic and hypereutectic Mg-Sn alloys were designed and studied as anodes for MRBs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results confirmed that these alloys contained unique microstructures consisting of α-Mg, Mg2Sn, and eutectic phases. The dissolution processes of the Mg-Sn alloys were studied in an all-phenyl-complex (APC) electrolyte. A multiple-step electrochemical dissolution process and a special adsorption interface layer were established for the Mg-Sn alloy anodes with an eutectic phase. Hypereutectic alloys with mixed phases showed better battery performance than the eutectic alloy owing to their superior mechanical properties. In addition, the morphology and Mg dissolution mechanism of the Mg-Sn alloys during the 1st dissolution process were characterized and discussed.

Enhanced interface stability of ammine magnesium borohydride by in situ decoration of MgBr2·2NH3 nanoparticles.

A novel Mg(BH4)2·1.9NH3-MgBr2·2NH3 composite was demonstrated as a solid-state Mg2+ electrolyte. The in situ decoration of MgBr2·2NH3 nanoparticles with an average size of 3.7 nm on the surface of Mg(BH4)2·1.9NH3 improves the Mg2+ conductivity to 2.1 × 10-4 S cm-1 at 50 °C and offers long-term stability towards the Mg metal anode.

Controllable synthesis of few-layer ammoniated 1T'-phase WS2 as an anode material for lithium-ion batteries.

Two-dimensional transition metal dichalcogenide (TMDC) nanosheets have received significant attention as anode materials for lithium-ion batteries, especially in their metallic 1T/1T' phase. However, controllable synthesis of few-layer 1T/1T' phase is still a challenge. In the present study, we report a facile two-step hydrothermal method to controllably synthesize few-layer 1T'-phase WS2. By tuning the redox-temperature of (NH4)2WS4 from 160 to 200 °C, the thickness of 1T'-phase WS2 can be adjusted from 4-6 to 20 layers. A higher reversible capacity is achieved in 1T'-phase WS2 with a smaller thickness, but the cycling stability decreases due to the lower crystallinity. The 1T'-phase WS2 synthesized by reduction of (NH4)2WS4 at 180 °C shows a moderate thickness of 10 layers and crystallinity, exhibiting the optimal Li-ion storage properties, i.e. a reversible capacity of 855.9 mA h g-1 at 100 mA g-1 and a good rate performance of 354.4 mA h g-1 at 5000 mA g-1. These results provide new insights into understanding the impacts of layer number on the Li-ion storage properties of 1T'-phase WS2.

Fast Room-Temperature Mg2+ Conductivity in Mg(BH4)2·1.6NH3-Al2O3 Nanocomposites.

Design of new functional materials with fast Mg-ion mobility is crucial for the development of competitive solid-state magnesium batteries. Herein, we present new nanocomposites, Mg(BH4)2·1.6NH3-Al2O3, reaching a high magnesium conductivity of σ(Mg2+) = 2.5 × 10-5 S cm-1 at 22 °C assigned to favorable interfaces between amorphous state Mg(BH4)2·1.6NH3; inert and insulating Al2O3 nanoparticles; and a minor fraction of crystalline material, mainly Mg(BH4)2·2NH3. Furthermore, quasi-elastic neutron scattering reveals that the Mg2+-ion mobility in the solid state appears to be correlated to relatively slow motion of NH3 molecules rather than the fast dynamics of BH4- complexes. The nanocomposite is compatible with a metallic Mg anode and shows stable Mg2+ stripping/plating in a symmetric cell and an electrochemical stability of ∼1.2 V. The nanocomposite has high mechanical stability and ductility and is a promising Mg2+ electrolyte for future solid-state magnesium batteries.

Size Effect of MgO on the Ionic Conduction Properties of a LiBH4·1/2NH3-MgO Nanocomposite.

A solid-state electrolyte (SSE) is the core component for fabricating solid-state batteries competitive with the currently commercial Li-ion batteries. In the present study, a LiBH4·1/2NH3-MgO nanocomposite has been developed as a fast Li-ion conductor. The conductive properties depend strongly on the size of MgO nanopowders. By adding MgO nanoparticles, the first-order transition at 55 °C observed in the crystalline LiBH4·1/2NH3 is suppressed due to the conversion of LiBH4·1/2NH3 into the amorphous state. When the size of MgO decreases from 163.6 to 13.9 nm, the MgO amount required for the phase-transition suppression of LiBH4·1/2NH3 decreases linearly from 92 to 75 wt %, accompanied by a significant enhancement of ionic conductivity. The optimized nanocomposite with 75 wt % MgO of size 13.9 nm exhibits a pronouncedly high conductivity of 4.0 × 10-3 S cm-1 at room temperature, which is 20 times higher than that of the crystalline LiBH4·1/2NH3. Furthermore, a smaller size MgO contributes to a higher electrochemical stability window (ESW) owing to the stronger interfacial interaction via B-O bonds, i.e., an ESW of 4.0 V is achieved with the addition of 75 wt % MgO of size 13.9 nm.

Li-Ion Conductivity Enhancement of LiBH4·xNH3 with In Situ Formed Li2O Nanoparticles.

Interfacial engineering is an efficient approach to improve the ionic conductivity of solid-state electrolytes. In the present study, we report the enhancement of in situ formed nanocrystalline Li2O on the thermal stability and electrochemical properties of amide lithium borohydride, LiBH4·xNH3 (x = 0.67-0.8). LiBH4·xNH3-Li2O composites with different amounts of Li2O are prepared by a one-step synthesis process by ball milling the mixture of LiBH4, LiNH2, and LiOH in molar ratios of 1:n:n (n = 1, 2, 3, 4). Owing to the strong interfacial effect with nanocrystalline Li2O, LiBH4·xNH3 is converted to the amorphous state in the presence of 78 wt % Li2O at n = 4. Consequently, the ionic conductivity of LiBH4·xNH3 at 20 °C is improved by orders of magnitude up to 5.4 × 10-4 S cm-1, the NH3 desorption temperature is increased by more than 20 °C, and the electrochemical window is widened from 0.5 to 3.8 V.

Heterostructured Ni3S2-Ni3P/NF as a Bifunctional Catalyst for Overall Urea-Water Electrolysis for Hydrogen Generation.

Urea oxidation reaction (UOR) has been proposed to replace the formidable oxygen evolution reaction (OER) to reduce the energy consumption for producing hydrogen from electrolysis of water owing to its much lower thermodynamic oxidation potential compared to that of the OER. Therefore, exploring a highly efficient and stable hydrogen evolution and urea electrooxidation bifunctional catalyst is the key to achieve economical and efficient hydrogen production. In this paper, we report a heterostructured sulfide/phosphide catalyst (Ni3S2-Ni3P/NF) synthesized via one-step thermal treatment of Ni(OH)2/NF, which allows the simultaneous occurrence of phosphorization and sulfuration. The obtained Ni3S2-Ni3P/NF catalyst shows a sheet structure with an average sheet thickness of ∼100 nm, and this sheet is composed of interconnected Ni3S2 and Ni3P nanoparticles (∼20 nm), between which there are a large number of accessible interfaces of Ni3S2-Ni3P. Thus, the Ni3S2-Ni3P/NF exhibits superior performance for both UOR and hydrogen evolution reaction (HER). For the overall urea-water electrolysis, to achieve current densities of 10 and 100 mA cm-2, cell voltage of only 1.43 and 1.65 V is required using this catalyst as both the anode and the cathode. Moreover, this catalyst also maintains fairly excellent stability after a long-term testing, indicating its potential for efficient and energy-saving hydrogen production. The theoretical calculation results show that the Ni atoms at the interface are the most efficient catalytically active site for the HER, and the free energy of hydrogen adsorption is closest to thermal neutrality, which is only 0.16 eV. A self-driven electron transfer at the interface, making the Ni3S2 sides become electron donating while Ni3P sides become electron withdrawing, may be the reason for the enhancement of the UOR activity. Therefore, this work shows an easy treatment for enhancing the catalytic activity of Ni-based materials to achieve high-efficiency urea-water electrolysis.

Iodine-Substituted Lithium/Sodium closo-Decaborates: Syntheses, Characterization, and Solid-State Ionic Conductivity.

Solid-state electrolytes based on closo-decaborates have caught increasing interest owing to the impressive room-temperature ionic conductivity, remarkable thermal/chemical stability, and excellent deformability. In order to develop new solid-state ion conductors, we investigated the influence of iodine substitution on the thermal, structural, and ionic conduction properties of closo-decaborates. A series of iodinated closo-decaborates, M2[B10H10-nIn] (M = Li, Na; n = 1, 2, 10), were synthesized and characterized by thermal analysis, powder X-ray diffraction, and electrochemical impedance spectroscopy; the stability and ionic conductivity of these compounds were studied. It was found that with the increase of iodine substitution on the closo-decaborate anion cage, the thermal decomposition temperature increases. All M2[B10H10-nIn] exhibit an amorphous structure. The ionic conductivity of Li2[B10H10-nIn] is higher than that of the Li2[B10H10] parent compound. An ionic conductivity of 2.96 × 10-2 S cm-1 with an activation energy of 0.23 eV was observed for Li2[B10I10] at 300 °C, implying that iodine substitution can improve the ionic conductivity. However, the ionic conductivity of Na2[B10H10-nIn] is lower than that of Na2[B10H10] and increases with the increase of iodine substitution, which could be associated with the increase of the electrostatic potential, mass, and volume of the iodinated anions. Moreover, Li2[B10I10] offers a Li-ion transference number of 0.999, an electrochemical stability window of 3.3 V and good compatibility with the Li anode, demonstrating its potential for application in high-temperature batteries.

Enhanced room temperature ionic conductivity of the LiBH4·1/2NH3-Al2O3 composite.

A novel LiBH4·1/2NH3-Al2O3 composite was demonstrated, in which amorphous LiBH4·1/2NH3 was in situ formed on the surface of Al2O3 owing to the strong interfacial interaction via B-O bonds. The ionic conductivity of LiBH4·1/2NH3 is improved by one order of magnitude to 10-3 S cm-1 and the electrochemical window up to 3.6 V.

Ammonium-Ammonia Complexes, N2H7+, in Ammonium closo-Borate Ammines: Synthesis, Structure, and Properties.

Metal closo-borates have recently received significant attention due to their potential applications as solid-state ionic conductors. Here, the synthesis, crystal structures, and properties of (NH4)2B10H10·xNH3 (x = 1/2, 1 (α and ß)) and (NH4)2B12H12·xNH3 (x = 1 and 2) are reported. In situ synchrotron radiation powder X-ray diffraction allows for the investigation of structural changes as a function of temperature. The structures contain the complex cation N2H7+, which is rarely observed in solid materials, but can be important for proton conductivity. The structures are optimized by density functional theory (DFT) calculations to validate the structural models and provide detailed information about the hydrogen positions. Furthermore, the hydrogen dynamics of the complex cation N2H7+ are studied by molecular dynamics simulations, which reveals several events of a proton transfer within the N2H7+ units. The thermal properties are investigated by thermogravimetry and differential scanning calorimetry coupled with mass spectrometry, revealing that NH3 is released stepwise, which results in the formation of (NH4)2BnHn (n = 10 and 12) during heating. The proton conductivity of (NH4)2B12H12·xNH3 (x = 1 and 2) determined by electrochemical impedance spectroscopy is low but orders of magnitude higher than that of pristine (NH4)2B12H12. The thermal stability of the complex cation N2H7+ is high, up to 170 °C, which may provide new possible applications of these proton-rich materials.

The mechanism of Mg2+ conduction in ammine magnesium borohydride promoted by a neutral molecule.

Light weight and cheap electrolytes with fast multi-valent ion conductivity can pave the way for future high-energy density solid-state batteries, beyond the lithium-ion battery. Here we present the mechanism of Mg-ion conductivity of monoammine magnesium borohydride, Mg(BH4)2·NH3. Density functional theory calculations (DFT) reveal that the neutral molecule (NH3) in Mg(BH4)2·NH3 is exchanged between the lattice and interstitial Mg2+ facilitated by a highly flexible structure, mainly owing to a network of di-hydrogen bonds, N-Hδ+-δH-B and the versatile coordination of the BH4- ligand. DFT shows that di-hydrogen bonds in inorganic matter and hydrogen bonds in bio-materials have similar bond strengths and bond lengths. As a result of the high structural flexibiliy, the Mg-ion conductivity is dramatically improved at moderate temperature, e.g. σ(Mg2+) = 3.3 × 10-4 S cm-1 at T = 80 °C for Mg(BH4)2·NH3, which is approximately 8 orders of magnitude higher than that of Mg(BH4)2. Our results may inspire a new approach for the design and discovery of unprecedented multivalent ion conductors.

Ammonia-assisted fast Li-ion conductivity in a new hemiammine lithium borohydride, LiBH4·1/2NH3.

Hemiammine lithium borohydride, LiBH4·1/2NH3, is characterized and a new Li+ conductivity mechanism is identified. It exhibits a Li+ conductivity of 7 × 10-4 S cm-1 at 40 °C in the solid state and 3.0 × 10-2 S cm-1 at 55 °C after melting. The molten state of LiBH4·1/2NH3 has a high viscosity and can be mechanically stabilized in nano-composites with inert metal oxides and other hydrides making it a promising battery electrolyte.

Potassium octahydridotriborate: diverse polymorphism in a potential hydrogen storage material and potassium ion conductor.

Octahydridoborate, i.e. [B3H8]- containing compounds, have recently attracted interest for hydrogen storage. In the present study, the structural, hydrogen storage, and ion conductivity properties of KB3H8 have been systematically investigated. Two distinct polymorphic transitions are identified for KB3H8 from a monoclinic (α) to an orthorhombic (α') structure at 15 °C via a second-order transition and eventually to a cubic (ß) structure at 30 °C by a first-order transition. The ß-polymorph of KB3H8 displays a high degree of disorder of the [B3H8]- anion, which facilitates increased cation mobility, reaching a K+ conductivity of ∼10-7 S cm-1 above 100 °C. ß-KB3H8 starts to release hydrogen at ∼160 °C, simultaneously with the release of B5H9 and trace amounts of B2H6. KBH4 and K3(BH4)(B12H12) are identified as crystalline decomposition products above 200 °C, and the formation of a KBH4 deficient structure of K3-x(BH4)1-x(B12H12) is observed at elevated temperature. The hydrogen-uptake properties of a KB3H8-2KH composite have been examined under 380 bar H2, resulting in the formation of KBH4 at T≥ 150 °C along with higher metal hydridoborates, i.e. K2B9H9, K2B10H10, and K2B12H12.

Post-Synthesis Amine Borane Functionalization of a Metal-Organic Framework and Its Unusual Chemical Hydrogen Release Phenomenon.

A novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation, utilizing gaseous diborane, is reported. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature, leading to the development of an unusual borenium type species (-NH=BH2+ ) ion-paired with a hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2 ) and the µ-iminodiborane (-µ-NHB2 H5 ) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H2 liberation.

Formation of CaB6 in the thermal decomposition of the hydrogen storage material Ca(BH4)2.

Using a combination of high resolution X-ray powder diffraction and X-ray Raman scattering spectroscopy at the B K- and Ca L2,3-edges, we analyzed the reaction products of Ca(BH4)2 after annealing at 350 °C and 400 °C under vacuum conditions. We observed the formation of nanocrystalline/amorphous CaB6 mainly and found only small contributions from amorphous B for annealing times larger than 2 h. For short annealing times of 0.5 h at 400 °C we observed neither CaB12H12 nor CaB6. The results indicate a reaction pathway in which Ca(BH4)2 decomposes to B and CaH2 and finally reacts to form CaB6. These findings confirm the potential of using Ca(BH4)2 as a hydrogen storage medium and imply the desired cycling capabilities for achieving high-density hydrogen storage materials.

In situ characterization of the decomposition behavior of Mg(BH4)2 by X-ray Raman scattering spectroscopy.

We present an in situ study of the thermal decomposition of Mg(BH4)2 in a hydrogen atmosphere of up to 4 bar and up to 500 °C using X-ray Raman scattering spectroscopy at the boron K-edge and the magnesium L2,3-edges. The combination of the fingerprinting analysis of both edges yields detailed quantitative information on the reaction products during decomposition, an issue of crucial importance in determining whether Mg(BH4)2 can be used as a next-generation hydrogen storage material. This work reveals the formation of reaction intermediate(s) at 300 °C, accompanied by a significant hydrogen release without the occurrence of stable boron compounds such as amorphous boron or MgB12H12. At temperatures between 300 °C and 400 °C, further hydrogen release proceeds via the formation of higher boranes and crystalline MgH2. Above 400 °C, decomposition into the constituting elements takes place. Therefore, at moderate temperatures, Mg(BH4)2 is shown to be a promising high-density hydrogen storage material with great potential for reversible energy storage applications.

A novel method for the synthesis of solvent-free Mg(B3H8)2.

This communication presents a novel and solvent-free method to synthesise Mg(B3H8)2 via the gas-solid reaction between B2H6 and Mg2NiH4, which overcomes the limitations of wet chemical methods requiring solvent removal.

A novel strategy for reversible hydrogen storage in Ca(BH4)2.

We report that decomposition pathway of Ca(BH4)2 can be efficiently controlled by reaction temperature. That is, it decomposes into CaB6 at a lower temperature range of 320 to 350 °C, but into amorphous boron at 400 to 450 °C. We identified the formation of CaB2H6 as the crucial intermediate step on the way to CaB6 that only forms at 320 to 350 °C.