Silica‐Protected Ultrathin Ni3FeN Nanocatalyst for the Efficient Hydrolytic Dehydrogenation of NH3BH3

Transition metal nitrides (TMNs) inevitably aggregate in the high‐temperature thermal ammonolysis process, resulting in blocking of the active catalytic sites and serious decreases in their corresponding catalytic performance. Therefore, how to synthesize ultrasmall TMNs with higher exposed unsaturated coordination sites is still a challenge. Herein, ultrathin Ni₃FeN (Ni₃FeN@SiO₂) with the size of ≈ 20 nm and thickness of ≈ 3.0 nm is fabricated by SiO₂ protection strategy. The obtained Ni₃FeN@SiO₂ displays outstanding performance in NH₃BH₃ hydrolytic dehydrogenation due to the high specific surface area, intrinsic metal‐vacancies, and hydrophilic SiO₂ layer.     

Graphene Layers‐Wrapped Fe/Fe5C2 Nanoparticles Supported on N‐doped Graphene Nanosheets for Highly Efficient Oxygen Reduction

Synthesis of highly efficient nonprecious metal electrocatalysts for the oxygen reduction reaction (ORR) superior to platinum (Pt) is still a big challenge. Herein, a new highly active ORR electrocatalyst is reported based on graphene layers‐wrapped Fe/Fe₅C₂ nanoparticles supported on N‐doped graphene nanosheets (GL‐Fe/Fe₅C₂/NG) through simply annealing a mixture of bulk graphitic carbon nitride (g‐C₃N₄) and ferrocene. An interesting exfoliation–denitrogen mechanism underlying the conversion of bulk g‐C₃N₄ into N‐doped graphene nanosheets is revealed. Owing to the high graphitic degree, optimum N‐doping level and sufficient active sites from the graphene layers‐wrapped Fe/Fe₅C₂ nanoparticles, the as‐prepared GL‐Fe/Fe₅C₂/NG electrocatalyst obtained at 800 °C exhibits outstanding ORR activity with a 20 mV more positive half‐wave potential than the commercial Pt/C catalyst in 0.1 m KOH solution and a comparable onset potential of 0.98 V. This makes GL‐Fe/Fe₅C₂/NG an outstanding electrocatalyst for ORR in alkaline solution.     

Near Ambient Condition Hydrogen Storage in a Synergized Tricomponent Hydride System

Reversible hydrogen storage over hydrides of light elements (HLEs) under ambient condition has been pursued actively for nearly two decades. However, because of unfavorable thermodynamics and/or severe kinetic barrier of HLEs, limited progress has been made. Here, it is demonstrated that the interaction of LiBH₄ with Mg(NH₂)₂ and LiH, three of the most investigated HLEs, can lead to a fully reversible dehydrogenation/rehydrogenation cycle at temperatures below 373 K. More importantly, with the desorption enthalpy of 24 kJ (mol H₂)^?1 the dehydrogenation process at 1.0 bar H₂ is theoretically possible to be as low as 266 K. Characterization of this combination of HLEs shows that LiBH₄ serves as a reagent complexing with intermediates and products of the dehydrogenation of Mg(NH₂)₂‐LiH, and significantly alters the overall thermodynamic and kinetic properties of the system.     

Boosting Polysulfide Redox Kinetics by Graphene‐Supported Ni Nanoparticles with Carbon Coating

Lithium–sulfur batteries have attracted extensive attention because of their high energy density. However, their application is still impeded by the inherent sluggish kinetics and solubility of intermediate products (i.e., polysulfides) of the sulfur cathode. Herein, graphene‐supported Ni nanoparticles with a carbon coating are fabricated by directly carbonizing a metal–organic framework/graphene oxide composite, which is then dispersed on a commercial glass fiber membrane to form a separator with electrocatalytic activity. In situ analysis and electrochemical investigation demonstrate that this modified separator can effectively suppress the shuttle effect and regulate the catalytic conversion of intercepted polysulfides, which is also confirmed by density functional theory calculations. It is found that Ni–C sites can chemically interact with polysulfides and stabilize the radical S₃^?? through Ni? S bonds to enable fast dynamic equilibrium with S₆^2?, while Ni nanoparticles reduce the oxidation barrier of Li₂S and accelerate ion/electron transport. As a result, the corresponding lithium–sulfur battery shows a high cycle stability (88% capacity retention over 100 cycles) even with a high sulfur mass loading of 8 mg cm^?2 and lean electrolyte (6.25 µ L mg^?1). Surprisingly, benefitting from the improved kinetics, the battery can work well at ?50 °C, which is rarely achieved by conventional Li–S batteries.     

Theoretical study of hydrogen storage in metal hydrides

Adsorption, absorption and desorption energies and other properties of hydrogen storage in palladium and in the metal hydrides AlH₃, MgH₂, Mg(BH₄)₂, Mg(BH₄)(NH₂) and LiNH₂ were analyzed. The DFT calculations on cluster models show that, at a low concentration, the hydrogen atom remains adsorbed in a stable state near the palladium surface. By increasing the hydrogen concentration, the tetrahedral and the octahedral sites are sequentially occupied. In the α phase the tetrahedral site releases hydrogen more easily than at the octahedral sites, but the opposite occurs in the β phase. Among the hydrides, Mg(BH₄)₂ shows the highest values for both absorption and desorption energies. The absorption energy of LiNH₂ is higher than that of the palladium, but its desorption energy is too high, a recurrent problem of the materials that have been considered for hydrogen storage. The release of hydrogen, however, can be favored by using transition metals in the material structure, as demonstrated here by doping MgH₂ with 3d and 4d-transition metals to reduce the hydrogen atomic charge and the desorption energy.     

Modeling of biopterin-dependent pathways of eNOS for nitric oxide and superoxide production

Endothelial dysfunction is associated with increase in oxidative stress and low NO bioavailability. The endothelial NO synthase (eNOS) uncoupling is considered an important factor in endothelial cell oxidative stress. Under increased oxidative stress, the eNOS cofactor tetrahydrobiopterin (BH₄) is oxidized to dihydrobiopterin, which competes with BH₄ for binding to eNOS, resulting in eNOS uncoupling and reduction in NO production. The importance of the ratio of BH₄ to oxidized biopterins versus absolute levels of total biopterin in determining the extent of eNOS uncoupling remains to be determined. We have developed a computational model to simulate the kinetics of the biochemical pathways of eNOS for both NO and O₂^•− production to understand the roles of BH₄ availability and total biopterin (TBP) concentration in eNOS uncoupling. The downstream reactions of NO, O₂^•−, ONOO⁻, O₂, CO₂, and BH₄ were also modeled. The model predicted that a lower [BH₄]/[TBP] ratio decreased NO production but increased O₂^•− production from eNOS. The NO and O₂^•− production rates were independent above 1.5 μM [TBP]. The results indicate that eNOS uncoupling is a result of a decrease in [BH₄]/[TBP] ratio, and a supplementation of BH₄ might be effective only when the [BH₄]/[TBP] ratio increases. The results from this study will help us understand the mechanism of endothelial dysfunction.     

Biopterin

Intraperitoneally injected [¹⁴C]biopterin (B), dihydrobiopterin (BH₂), and tetrahydrobiopterin (BH₄) penetrated the brain rapidly, but in amounts sufficient to represent only a minor source of supply. Unlike isobiopterin, B was rapidly reduced to BH₂ in brain. The distribution of BH₄ and BH₂, but not of B, could be correlated with the tryptophan and tyrosine hydroxylase activity of various cerebral areas. In the whole brain, the sizes of pools were 0.117 for B, 0.204 for BH₂, and 0.341 g/g for BH₄, while the cerebral turnover rates of B, BH₂, and BH₄ were 0.25, 0.43, and 0.71 nmol/g per h, respectively. From birth through development, the cerebral levels of B remained constant, whereas the levels of the reduced biopterins increased. After subcellular fractionation, 65% of the biopterins (B, BH₂, and BH₄) were recovered from the supernatant. Of the organelles, microsomes contained the largest concentration of pterins. About 1/6 of all pterins in the brain was present in the synaptosomes.     

Tailored Electron Transfer Pathways in Aucore/Ptshell–Graphene Nanocatalysts for Fuel Cells

Au_core/Pt_shell–graphene catalysts (G‐Cys‐Au@Pt) are prepared through chemical and surface chemical reactions. Au–Pt core–shell nanoparticles (Au@Pt NPs) covalently immobilized on graphene (G) are efficient electrocatalysts in low‐temperature polymer electrolyte membrane fuel cells. The 9.5 ± 2 nm Au@Pt NPs with atomically thin Pt shells are attached on graphene via l ‐cysteine (Cys), which serves as linkers controlling NP loading and dispersion, enhancing the Au@Pt NP stability, and facilitating interfacial electron transfer. The increased activity of G‐Cys‐Au@Pt, compared to non‐chemically immobilized G‐Au@Pt and commercial platinum NPs catalyst (C‐Pt), is a result of (1) the tailored electron transfer pathways of covalent bonds integrating Au@Pt NPs into the graphene framework, and (2) synergetic electronic effects of atomically thin Pt shells on Au cores. Enhanced electrocatalytic oxidation of formic acid, methanol, and ethanol is observed as higher specific currents and increased stability of G‐Cys‐Au@Pt compared to G‐Au@Pt and C–Pt. Oxygen reduction on G‐Cys‐Au@Pt occurs at 25 mV lower potential and 43 A g_Pt^?1 higher current (at 0.9 V vs reversible hydrogen electrode) than for C–Pt. Functional tests in direct fomic acid, methanol and ethanol fuel cells exhibit 95%, 53%, and 107% increased power densities for G‐Cys‐Au@Pt over C–Pt, respectively.     

An Ultralong Lifespan and Low‐Temperature Workable Sodium‐Ion Full Battery for Stationary Energy Storage

Presently, commercialization of sodium‐ion batteries (SIBs) is still hindered by the relatively poor energy‐storage performance. In addition, low‐temperature (low‐T) Na storage is another principal concern for the wide application of SIBs. Unfortunately, the Na‐transfer kinetics is extremely sluggish at low‐T, as a result, there are few reports on low‐T SIBs. Here, an advanced low‐T sodium‐ion full battery (SIFB) assembled by an anode of 3D Se/graphene composite and a high‐voltage cathode (Na₃V₂(PO₄)₂O₂F) is developed, exhibiting ultralong lifespan (over even 15 000 cycles, the capacity retention is still up to 86.3% at 1 A g^?1), outstanding low‐T energy storage performance (e.g., all values of capacity retention are >75% after 1000 cycles at temperatures from 25 to ?25 °C at 0.4 A g^?1), and high‐energy/power properties. Such ultralong lifespan signifies that the developed sodium‐ion full battery can be used for longer than 60 years, if batteries charge/discharge once a day and 80% capacity retention is the standard of battery life. As a result, the present study not only promotes the practicability and commercialization of SIBs but also points out the new developing directions of next‐generation energy storage for wider range applications.     

Reductive openings of benzylidene acetals. Kinetic studies of borane and alane activation by Lewis acids

The reaction kinetics for a number of reductive openings of methyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-d-glucopyranoside have been investigated. Openings to give free HO-6 (using BH₃·THF-AlCl₃-THF or LiAlH₄-AlCl₃-Et₂O) follow first order kinetics, while reactions yielding free HO-4 (using BH₃·NMe₃-AlCl₃-THF or BH₃·NMe₃-BF₃·OEt₂-THF) follow higher order kinetics. The addition of water to the BH₃·NMe₃-AlCl₃-THF results in faster reactions. The BH₃·SMe₂-AlCl₃-THF system constitutes a borderline case, yielding both free HO-6 (by a first order reaction) and free HO-4 (by a higher order reaction). These results correlate well with the concept of regioselectivity by activation of borane complexes.     

Crystallographic characterization of the α,γ C12 helix in hybrid peptide sequences

The solid‐state conformations of two αγ hybrid peptides Boc‐[Aib‐γ⁴(R)Ile]₄‐OMe 1 and Boc‐[Aib‐γ⁴(R)Ile]₅‐OMe 2 are described. Peptides 1 and 2 adopt C₁₂‐helical conformations in crystals. The structure of octapeptide 1 is stabilized by six intramolecular 4 → 1 hydrogen bonds, forming 12 atom C₁₂ motifs. The structure of peptide 2 reveals the formation of eight successive C₁₂ hydrogen‐bonded turns. Average backbone dihedral angles for αγ C₁₂ helices are peptide 1 , Aib; φ (°) = ?57.2 ± 0.8, ψ (°) = ?44.5 ± 4.7; γ⁴(R)Ile; φ (°) = ?127.3 ± 7.3, θ₁ (°) = 58.5 ± 12.1, θ₂ (°) = 67.6 ± 10.1, ψ (°) = ?126.2 ± 16.1; peptide 2 , Aib; φ (°) = ?58.8 ± 5.1, ψ (°) = ?40.3 ± 5.5; ψ⁴(R)Ile; φ (°) = ?123.9 ± 2.7, θ₁ (°) = 53.3 θ 4.9, θ ₂ (°) = 61.2 ± 1.6, ψ (°) = ?121.8 ± 5.1. The tendency of γ⁴‐substituted residues to adopt gauche–gauche conformations about the C^α–C^β and C^β–C^γ bonds facilitates helical folding. The αγ C₁₂ helix is a backbone expanded analog of α peptide 3₁₀ helix. The hydrogen bond parameters for α peptide 3₁₀ and α‐helices are compared with those for αγ hybrid C₁₂ helix. Copyright © 2016 European Peptide Society and John Wiley & Sons.     

Synthesis and thermal stability of Zr(BH4)4 and Zr(BD4)4 produced by mechanochemical processing

Zirconium tetrahydroborate Zr(BH₄)₄ and its deuteride compound Zr(BD₄)₄ were successfully synthesized by mechanochemical reaction between NaBH₄ or NaBD₄ and ZrCl₄, reaching yields of 55% and 46%, respectively. The influence of the synthesis parameters on the yield of Zr(BH₄)₄ was analyzed. The composition of the ZrCl₄:NaBH₄ starting mixture and the use of LiBH₄ instead of NaBH₄ as reactive show a clear effect on the Zr(BH₄)₄ yield. Instead, milling atmosphere does not affect the amount of the obtained product. FTIR analysis of atmosphere inside of milling vial allows to determine the formation of diborane during milling from Zr(BH₄)₄ decomposition. Thermal stability of pure Zr(BH₄)₄ and its deuterated compound was studied by combined gas-phase FTIR and DSC measurements under flowing Ar. We found that Zr(BH₄)₄/Zr(BD₄)₄ melt at about 305/303 K, decompose at about 430 K from the gas-phase and show evolution of B₂H₆/B₂D₆ under heating.     

Effect of different temperatures to remove reduction gas on the photoluminescence properties of Eu‐doped Li2(Ba1‐xSrx)SiO4 phosphors

In this study, Eu‐doped Li₂(Ba_1‐xSr_x)SiO₄ powders (x = 0, 0.2, 0.4, and 0.6) were synthesized at 850°C in a reduction atmosphere (5% H₂ + 95% N₂) for a duration of 1 h using a solid‐state reaction method. The reduction atmosphere was infused as the synthesis temperature reached 850°C, and was removed as the temperature dropped to 800–500°C. Li₂(Ba_1‐xSr_x)SiO₄ (or Li₂BaSiO₄), (Ba,Sr)₂SiO₄ (or BaSiO₄), and Li₄SiO₄ phases co‐existed in the synthesized Eu‐doped Li₂(Ba_1‐xSr_x)SiO₄ powders. A new finding was that the reduction atmosphere removing (RAR) temperature of the Li₂(Ba_1‐xSr_x)SiO₄ phosphors had a large effect on their photoluminescence excitation (PLE) and PL properties. Except for the 800°C‐RAR‐treated Li₂BaSiO₄ phosphor, PLE spectra of all other Li₂(Ba_1‐xSr_x)SiO₄ phosphors had one broad emission band with two emission peaks centred at ~242 and ~283 nm; these PL spectra had one broad emission band with one emission peak centred at 502–514 nm. We showed that the 800°C‐RAR‐treated Li₂BaSiO₄ phosphor emitted a red light and all other Li₂(Ba_1‐xSr_x)SiO₄ phosphors emitted a green light. Reasons for these results are discussed thoroughly.     

Low‐Temperature Reduction Strategy Synthesized Si/Ti3C2 MXene Composite Anodes for High‐Performance Li‐Ion Batteries

Silicon is attracting enormous attention due to its theoretical capacity of 4200 mAh g^?1 as an anode for Li‐ion batteries (LIBs). It is of fundamental importance and challenge to develop low‐temperature reaction route to controllably synthesize Si/Ti₃C₂ MXene LIBs anodes. Herein, a novel and efficient strategy integrating in situ orthosilicate hydrolysis and a low‐temperature reduction process to synthesize Si/Ti₃C₂ MXene composites is reported. The hydrolysis of tetraethyl orthosilicate leads to homogenous nucleation and growth of SiO₂ nanoparticles on the surface of Ti₃C₂ MXene. Subsequently, SiO₂ nanoparticles are reduced to Si via a low‐temperature (200 °C) reduction route. Importantly, Ti₃C₂ MXene not only provides fast transfer channels for Li⁺ and electrons, but also relieves volume expansion of Si during cycling. Moreover, the characteristics of excellent pseudocapacitive performance and high conductivity of Ti₃C₂ MXene can synergistically contribute to the enhancement of energy storage performance. As expected, Ti₃C₂/Si anode exhibits an outstanding specific capacity of 1849 mAh g^?1 at 100 mA g^?1, even retaining 956 mAh g^?1 at 1 A g^?1. The low‐temperature synthetic route to Si/Ti₃C₂ MXene electrodes and involved battery‐capacitive dual‐model energy storage mechanism has potential in the design of novel high‐performance electrodes for energy storage devices.     

CoNi2S4‐Graphene‐2D‐MoSe2 as an Advanced Electrode Material for Supercapacitors

3D CoNi₂S₄‐graphene‐2D‐MoSe₂ (CoNi₂S₄‐G‐MoSe₂) nanocomposite is designed and prepared using a facile ultrasonication and hydrothermal method for supercapacitor (SC) applications. Because of the novel nanocomposite structures and resultant maximized synergistic effect among ultrathin MoSe₂ nanosheets, highly conductive graphene and CoNi₂S₄ nanoparticles, the electrode exhibits rapid electron and ion transport rate and large electroactive surface area, resulting in its amazing electrochemical properties. The CoNi₂S₄‐G‐MoSe₂ electrode demonstrates a maximum specific capacitance of 1141 F g^?1, with capacitance retention of ≈108% after 2000 cycles at a high charge–discharge current density of 20 A g^?1. As to its symmetric device, 109 F g^?1 at a scan rate of 5 mV s^?1 is exhibited. This pioneering work should be helpful in enhancing the capacitive performance of SC materials by designing nanostructures with efficient synergetic effects.     

Oxidative folding of ω-conotoxin MVIIC: Effects of temperature and salt

Oxidative folding of o-conotoxin MVIIC, a highly basic 26-amino acid peptide with three disulfide bonds, predominantly gave two products with mismatched disulfide bonds in 0.1M NH₄OAc buffer (pH 7.7) at 21°C both in the presence and absence of redox reagents such as reduced and oxidized glutathione. A low reaction temperature (5°C) and a high salt concentration in buffer such as 2M (NH₄)₂SO₄ were necessary to obtain the correctly folded biologically active product. The folding reaction was found to proceed via a two-stage pathway of (I) the formation and (II) the rearrangement of the mismatched disulfide bonds. Both the reaction temperature and the salt strongly affected the equilibrium between mismatched and correctly formed disulfide bonds in the second stage. Such an effect of salts on the rearrangement reaction could be explained by anion binding at a low concentration and the salting out effect at a high concentration by analyzing the rank order of their effectiveness. The anion-binding effect was also confirmed by examining the folding of the tetra-acetylated peptide at the Lys side chains. CD study suggested that the yield of the biologically active product was correlated with its conformational change as functions of temperature and salt concentration. © 1996 John Wiley & Sons, Inc.     

Luminescence characterization of Dy and Eu doped Na6Mg(SO4)4 phosphors

A series of single‐phase phosphors based on Na₆Mg(SO₄)₄ (Z_eff = 11.70) doped with Dy and Eu was prepared by the wet chemical method. The photoluminescence (PL) and thermoluminescence (TL) properties of Dy³⁺‐ and Eu³⁺‐activated Na₆Mg(SO₄)₄ phosphors were investigated. The characteristic emissions of Dy³⁺ and Eu³⁺ were observed in the Na₆Mg(SO₄)₄ host. The TL glow curve of the Na₆Mg(SO₄)₄:Dy phosphor consisted of a prominent peak at 234°C and a very small hump at 158°C. The TL sensitivity of the Na₆Mg(SO₄)₄:Dy phosphor was found to be four times less than the commercialized CaSO₄:Dy phosphor. The TL dose–response of the Na₆Mg(SO₄)₄:Dy phosphor was studied from a dose range of 5–10 kGy and the linear dose–response was observed up to 1 kGy which is good for a microcrystalline phosphor. Trapping parameters for both the samples were calculated using the Initial Rise and Chen's peak shape methods.     

Oxidation of tetrahydrobiopterin by peroxynitrite or oxoferryl species occurs by a radical pathway

The molecular mechanisms of tetrahydrobiopterin (BH₄) oxidation by peroxynitrite (ONOO^-) was studied using ultra-weak chemiluminescence, electron paramagnetic resonance (EPR) and UV-visible diodearray spectrophotometry, and compared to BH₄ oxidation by oxoferryl species produced by the myoglobin/hydrogen peroxide (Mb/H₂O₂) system. The oxidation of BH₄ by ONOO^- produced a weak chemiluminescence, which was altered by addition of 50 mM of the spin trap α-(4-pyridyl-1-oxide)-N-tert butylnitrone (POBN). EPR spin trapping demonstrated that the reaction occurred at least in part by a radical pathway. A mixture of two spectra composed by an intense six-line spectrum and a fleeting weak nine-line one was observed when using ONOO^-. Mb/H₂O₂ produced a short-living light emission that was suppressed by the addition of BH₄. Simultaneous addition of POBN, BH₄ and Mb/H₂O₂ produced the same six-line EPR spectrum, with a signal intensity depending on BH₄ concentration. Spectrophotometric studies confirmed the rapid disappearance of the characteristic peak of ONOO^- (302 nm) as well as substantial modifications of the initial BH₄ spectrum with both oxidant systems. These data demonstrated that BH₄ oxidation, either by ONOO^- or by Mb/H₂O₂, occurred with the production of activated species and by radical pathways.     

A Heterogeneous Carbon Nitride–Nickel Photocatalyst for Efficient Low‐Temperature CO2 Methanation

The Sabatier reaction, i.e., the hydrogenation of CO₂ to methane (CH₄) using hydrogen (H₂), constitutes a potentially scalable method to store energy in a product with a high energy density. However, up to today, this reaction has been mainly thermally driven and conducted at high temperatures (typically 400–600 °C). Using light as a renewable energy source will allow for a more sustainable process by lowering the reaction temperature. Here, it is demonstrated that Ni nanoparticles support on graphitic carbon nitride (g‐CN) are a highly efficient and stable photocatalyst for the gas‐phase CO₂ methanation at low temperature (150 °C). Detailed mechanistic studies reveal a very low activation energy for the reaction and high activity under visible light, leading to a remarkable and continuous CH₄ production of 28 µmol g^?1 h^?1 of CH₄ for 24 h.     

In Situ,Fast, High‐Temperature Synthesis of Nickel Nanoparticles in Reduced Graphene Oxide Matrix

For the first time, a fast heating–cooling process is reported for the synthesis of carbon‐coated nickel (Ni) nanoparticles on a reduced graphene oxide (RGO) matrix (nano‐Ni@C/RGO) as a high‐performance H₂O₂ fuel catalyst. The Joule heating temperature can reach up to ≈2400 K and the heating time can be less than 0.1 s. Ni microparticles with an average diameter of 2 µm can be directly converted into nanoparticles with an average diameter of 75 nm. The Ni nanoparticles embedded in RGO are evaluated for electro‐oxidation performance as a H₂O₂ fuel in a direct peroxide–peroxide fuel cell, which exhibits an electro‐oxidation current density of 602 mA cm^?2 at 0.2 V (vs Ag/AgCl), ≈150 times higher than the original Ni microparticles embedded in the RGO matrix (micro‐Ni/RGO). The high‐temperature, fast Joule heating process also leads to a 4–5 nm conformal carbon coating on the surface of the Ni nanoparticles, which anchors them to the RGO nanosheets and leads to an excellent catalytic stability. The newly developed nano‐Ni@C/RGO composites by Joule heating hold great promise for a range of emerging energy applications, including the advanced anode materials of fuel cells.