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1.
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.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
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 S62?, 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.  相似文献   

5.
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.  相似文献   

6.
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.  相似文献   

7.
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.  相似文献   

8.
Aucore/Ptshell–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 gPt?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.  相似文献   

9.
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.  相似文献   

10.
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.  相似文献   

11.
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 Cα–Cβ and Cβ–Cγ 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.  相似文献   

12.
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.  相似文献   

13.
In this study, Eu‐doped Li2(Ba1‐xSrx)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(Ba1‐xSrx)SiO4 (or Li2BaSiO4), (Ba,Sr)2SiO4 (or BaSiO4), and Li4SiO4 phases co‐existed in the synthesized Eu‐doped Li2(Ba1‐xSrx)SiO4 powders. A new finding was that the reduction atmosphere removing (RAR) temperature of the Li2(Ba1‐xSrx)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(Ba1‐xSrx)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(Ba1‐xSrx)SiO4 phosphors emitted a green light. Reasons for these results are discussed thoroughly.  相似文献   

14.
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.  相似文献   

15.
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.  相似文献   

16.
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.  相似文献   

17.
A series of single‐phase phosphors based on Na6Mg(SO4)4 (Zeff = 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.  相似文献   

18.
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.  相似文献   

19.
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.  相似文献   

20.
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.  相似文献   

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