Effects of synthesis conditions on layered Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2 positive-electrode via hydroxide co-precipitation method for lithium-ion batteries

Layered Li[Ni1/3Co1/3Mn1/3]O2 was synthesized with complex metal hydroxide precursors that were prepared by a co-precipitation method.The influence of coordination between ammonia and transition-metal cations on the structural and electrochemical properties of the Li[Ni1/3Co1/3Mn1/3]O2 materials was studied.It is found that when the molar ratio of ammonia to total transition-metal cations is 2.7：1,uniform particle size distribution of the complex metal hydroxide is observed via scanning electron microscopy.The average particle size of Li[Ni1/3Co1/3Mn1/3]O2 materials was measured to be about 500 nm,and the tap-density was measured to be approximately 2.37 g/cm3,which is comparable with that of commercialized LiCoO2.XRD analysis indicates that the presently synthesized Li[Ni1/3Co1/3Mn1/3]O2 has a hexagonal layered-structure.The initial discharge capacity of the Li[Ni1/3Co1/3Mn1/3]O2 positive-electrode material is determined to be 181.5 mA·h/g using a Li/Li[Ni1/3Co1/3Mn1/3]O2 cell operated at 0.1C in the voltage range of 2.8-4.5 V.The discharge capacity at the 50th cycle at 0.5C is 170.6 mA·h/g.

边缘修饰对锗烯纳米带电子结构的影响

本工作利用第一性原理研究了氢化效应对扶手椅型锗烯纳米带(AGeNRs)几何结构和电子结构的影响,分别计算了几何结构与稳定性、能带结构以及态密度,研究了形成能和能带结构随各种带宽度函数的变化。通过增加带的宽度,AGeNRs的带隙尺寸根据三种不同的趋势减小。基于这些趋势,可以将其分为三类,分别命名为N=3P、N=3P+1、N=3P+2,N是宽度上的锗原子数,P是整数。研究表明,裸露边缘的AGeNRs稳定性较低,氢化处理可以提高纳米带的稳定性,其中双氢化结构的稳定性最高。其次,边缘利用H原子进行修饰后,电荷密度发生转移,整个材料的电子和光学特性发生变化,说明边缘效应影响其电学和光学性质。对于裸露边缘和单氢化方式,其带隙符合N=3P+2>N=3P>N=3P+1;而对于双氢化处理和单氢化-双氢化的混合结构,其带隙符合N=3P>N=3P+1>N=3P+2。由于纳米带都是直接带隙,可以推测此类AGeNRs可能适用于光学领域,而且其电子和光学性质可以通过纳米带宽度以及氢化方式在很宽的范围内进行调节。

原子光谱/质谱分析中蒸气发生法进样的非传统技术的研究

报道了在原子光谱 /质谱分析中化学蒸气发生法进样方面的一些最新研究成果 ,包括镍的蒸气发生法的研究 ,共氢化增感效应的研究 ,氢化物发生气相富集技术的研究等 ,以及利用现代质谱技术实现对可形成氢化物元素化学形态直接测定的可行性的探讨 .

Hydrogenation and Ammoniation of SrTiO3 for an Enhanced Visible-light Photocatalysis

Hydrogenation and ammoniation of SrTiOa （STO）, a normal ultraviolet photocatalyst, were performed by annealing STO（100） in Hz：N2=5%：95% and NH3, respectively, at various temperatures T. It was found that hydrogenation at T≥900℃ remarkably enhanced the UV photocatalytic ability of STO, but the visible-light photocatalysis was still unavailable, while ammoniation at T≥800℃ introduced the N doping, resulting in visible-light photocat- alytie activity. Furthermore, when a hydrogenated STO was subjected to ammoniation, the visible-light photocatalytie ability was nearly the same as that of the ammoniated one; but the hydrogenation of an ammoniated one significantly enhanced visible-light photoeatalysis, indicating a synergetic effect of hydrogenation and ammoniation. Discussions and identifications have been made to analyze these results.

Electrochemical hydrogen storage characteristics of Ti_(0.10)Zr_(0.15)V_(0.35)Cr_(0.10)Ni_(0.30)-10% LaNi_3 composite and its synergetic effect

Hydrogen storage composite alloy Ti0.10Zr0.15V0.35Cr0.10Ni0.30–10% LaNi3 was prepared by two-step arc-melting to improve the electro-catalytic activity and the kinetic performance of Ti-V-based solid solution alloy. The electrochemical properties and synergetic effect of the composite alloy electrode were systematically investigated by using X-ray diffractometry, field emission scanning electron microscopy, energy-dispersive spectrometry, electrochemical impedance spectroscopy and galvanostatic charge/discharge test. It is found that the main phase of the composite alloy is composed of V-based solid solution phase with a BCC structure and C14 Laves phase with hexagonal structure, while the secondary phase is formed in the composite alloy. The comprehensive electrochemical properties of the composite alloy electrode are significantly improved. The activation cycle number, the maximum discharge capacity and the low temperature dischargeability of the composite alloy are 5 cycles, 362.5 mA-h/g and 65.84% at 233 K, respectively. It is suggested that distinct synergetic effect occurs in the activation process, composite process, cyclic process and discharge process at a low or high temperature under different current densities, in the charge–transfer resistance and exchange current density.

Carbon supported IrM(M= Fe,Ni,Co) alloy nanoparticles for the catalysis of hydrogen oxidation in acidic and alkaline medium

We studied the alloying effect in lr-based alloys on the catalysis of the hydrogen oxidation reaction （HOP,） in both acidic and alkaline medium. IrFe, lrNi and IrCo alloy catalysts with nanoparticle size of 〈S nm were obtained by our solvent-vaporization plus hydrogen reduction method. The second metal played an important role in tuning the crystal structure and surface electronic structure of the Ir-based alloy catalyst. Among the lrFe, IrCo and lrNi alloy catalysts, Ni induced a mid-sized contrac- tion of the lr lattice, and gave the best HOR activity in both acidic and alkaline medium. In acidic medium, the weakening of the Ir-Had interaction caused by the electronic effect of M （M = Fe, Ni, Co） alloying is responsible for the enhancement of HOR activity. The oxophilic effect of the catalytic metal surface, which affects OHad adsorption and desorption and surface Had coverage, has a large impact on the HOR activity in the case of alkaline medium,

Construction of LSPR-enhanced 0D/2D CdS/MoO3‒x S-scheme heterojunctions for visible-light-driven photocatalytic H2 evolution

Plasmonic nonmetal semiconductors with localized surface plasmon resonance(LSPR)effects possess extended light-response ranges and can act as highly efficient H2 generation photocatalysts.Herein,an LSPR-enhanced 0D/2D CdS/MoO3‒x heterojunction has been synthesized by the growth of 0D CdS nanoparticles on 2D plasmonic MoO3‒x elliptical nanosheets via a simple coprecipitation method.Taking advantage of the LSPR effect of the MoO3‒x elliptical nanosheets,the light absorption of the CdS/MoO3‒x heterojunction was extended from 600 nm to the near-infrared region(1400 nm).Furthermore,the introduction of 2D plasmonic MoO3‒x elliptical nanosheets not only provided a platform for the growth of CdS nanoparticles,but also contributed to the construction of an LSPR-enhanced S-scheme structure due to the interface between the MoO3‒x and CdS,accelerating the separation of light-induced electrons and holes.Therefore,the CdS/MoO3‒x heterojunction exhibited higher photocatalytic H2 generation activity than pristine CdS under visible light irradiation,including under 420,450,550,and 650 nm monochromic light,as well as improved photo-corrosion performance.

Effect of In_(2)O_(3)particle size on CO_(2) hydrogenation to lower olefins over bifunctional catalysts

A reaction-coupling strategy is often employed for CO_(2)hydrogenation to produce fuels and chemicals using oxide/zeolite bifunctional catalysts.Because the oxide components are responsible for CO_(2)activation,understanding the structural effects of these oxides is crucial,however,these effects still remain unclear.In this study,we combined In_(2)O_(3),with varying particle sizes,and SAPO‐34 as bifunctional catalysts for CO_(2)hydrogenation.The CO_(2)conversion and selectivity of the lower olefins increased as the average In_(2)O_(3)crystallite size decreased from 29 to 19 nm;this trend mainly due to the increasing number of oxygen vacancies responsible for CO_(2) and H_(2) activation.However,In_(2)O_(3)particles smaller than 19 nm are more prone to sintering than those with other sizes.The results suggest that 19 nm is the optimal size of In_(2)O_(3)for CO_(2)hydrogenation to lower olefins and that the oxide particle size is crucial for designing catalysts with high activity,high selectivity,and high stability.

Recent advances in heterogeneous catalytic hydrogenation and dehydrogenation of N-heterocycles

The selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines(py-THQ) and its derivatives has attracted a considerable amount of attention as they show great versatility in many pharmaceuticals, agrochemicals, and fine chemicals. Over the past few decades, great breakthroughs have been achieved in the controlled synthesis of efficient heterogeneous catalysts used for the selective hydrogenation of functionalized quinoline compounds, which allow one to correlate the structure-property relationships. In this review, we will summarize the recent significant progress achieved in this field covering the synthetic strategies, microstructural and chemical features, catalytic performance, and internal relationships. State-of-the-art noble metal-based single(Pd, Pt, Ru, Rh, Ir and Au) and bi/multi-metallic catalysts(RuCu, AuPd, and PdNi) are first introduced, followed by a summary of earth-abundant metal-based catalysts(Co, Fe, Ni, and Cu). Finally, the dehydrogenation of N-heterocycles is introduced to form a reversible hydrogenation/dehydrogenation system for H2 storage, which can be employed in a liquid organic hydrogen system. Furthermore, the reaction mechanism and future research direction in these areas are also discussed. This review will deepen our understanding of the catalytic transformation of N-heterocycles and provide guidance for researchers on the rational design of catalysts.

Hydrodeoxygenation of Phenolic Model Compounds over MoS2 Catalysts with Different Structures

Several MoS2 catalysts of different structure, prepared by in situ decomposition of ammonium heptamolybdate （AHM） and molybdenum naphthenate （MoNaph）, and by MoS2 exfoliation （TDM）, were characterized by BET, X-ray diffraction （XRD）, Energy Dispersive X-ray （EDX） and transmission electron microscopy （TEM）. The analysis showed that MoS2 structure was dependant upon the preparation procedure. The activity of the catalysts was determined by measuring the hydrodeoxygenation （HDO） of phenol, 4-methylphenol and 4-methoxyphenol using a batch autoclave reactor operated at 2.8 MPa of hydrogen and temperatures ranging from 320-370℃. By comparing the conversion, the reactivity order of the catalysts was： AHM〉TDM-D〉MoNaph〉thermal〉MoS2 powder〉 TDM-W. Also, the effect of reaction temperature on the HDO conversion was explained in terms of equilibrium of reversible reaction kinetics. The main products of the HDO for phenolic compounds were identified by gas chromatography/mass spectrometry （GC/MS）. The results showed that the product distribution and the HDO selectivity were correlated with the reaction temperature. Two parallel reaction routes, direct hydrogenolysis and combined hydrogenation-hydrogenolysis, were confirmed by the analysis of the product distribution. High temperature favored hydrogenolysis over hydrogenation for HDO of phenol and 4-methoxyphenol, whereas for 4-methylphenol the reverse was true.

Enhanced photocatalytic H_(2) production performance of CdS hollow spheres using C and Pt as bi-cocatalysts

Photocatalytic H2 production from water splitting is an effective method to solve energy crisis and environmental pollution simultaneously.Herein,carbon@CdS composite hollow spheres(C@CdS-HS)are fabricated via a facile hydrothermal method using porous carbon hollow spheres(C-HS)as the template.The C@CdS-HS shows an excellent photocatalytic H2-generation rate of 20.9 mmol h^(−1) g^(−1)(apparent quantum efficiency of 15.3%at 420 nm),with 1.0 wt%Pt as a cocatalyst under simulated sunlight irradiation;this rate is 69.7,13.9,and 3.9 times higher than that obtained with pure CdS hollow spheres(CdS-HS),C@CdS-HS,and CdS-HS/Pt,respectively.The enhanced photocatalytic H_(2)-evolution activity of C@CdS-HS/Pt is due to the synergistic effect of C and Pt as the bi-cocatalyst.The C-HS serves not only as an active site provider but also as an electron transporter and reservoir.Moreover,C-HS has a strong photothermal effect that is induced by near infrared light,which kinetically accelerates the H_(2)-production reaction.Additionally,the underlying charge transfer pathway and process from CdS to C−HS is revealed.This work highlights the potential application of C-HS-based nanocomposites in solar-to-chemical energy conversion.

SiO_2-supported Au-Ni bimetallic catalyst for the selective hydrogenation of acetylene

Supported Au catalysts have been reported to exhibit high ethylene selectivity in the hydrogenation of acetylene,but the conversion is relatively low.Adding a second metal to Au has proven to be a promising approach to enhance its catalytic performance in acetylene hydrogenation.In this work,SiO2‐supported Au‐Ni bimetallic catalysts were synthesized and investigated in the selective hydrogenation of acetylene.The Au‐Ni bimetallic catalysts exhibited much higher catalytic performance than that of the corresponding monometallic Au or Ni catalysts.By tuning the reduction temperature and/or Ni loading,we obtained an Au‐Ni/SiO2catalyst with optimal performance.The results of transmission electron microscopy imaging revealed that the Au‐Ni bimetallic particles were highly dispersed on the SiO2support.Meanwhile,analysis of the bimetallic catalyst by energy‐dispersive X‐ray spectroscopy,high‐resolution transmission electron microscopy,and in situ diffuse reflectance infrared Fourier transform spectroscopy demonstrated the formation of Au‐Ni alloy,which contributed to the synergistic effect between Au and Ni in the hydrogenation of acetylene.

Facet dependence of electrocatalytic furfural hydrogenation on palladium nanocrystals

Electrocatalytic hydrogenation(ECH)offers a sustainable route for the conversion of biomass-derived feedstocks under ambient conditions;however,an atomic-level understanding of the catalytic mechanism based on heterogeneous electrodes is lacking.To gain insights into the relation between electrocatalysis and the catalyst surface configuration,herein,the facet dependence of the ECH of furfural(FAL)is investigated on models of nanostructured Pd cubes,rhombic dodecahedrons,and octahedrons,which are predominantly enclosed by{100},{110},and{111}facets,respectively.The facet-dependent specific activity to afford furfuryl alcohol(FOL)follows the order of{111}>{100}>{110}.Experimental and theoretical kinetic analyses confirmed the occurrence of a competitive adsorption Langmuir-Hinshelwood mechanism on Pd,in which the ECH activity can be correlated with the difference between the binding energies of chemisorbed H(^(*)H)and FAL(^(*)FAL)based on density functional theoretical(DFT)calculations.Among the three facets,Pd{111}exhibiting the strongest^(*)H but the weakest^(*)FAL showed the copresence of the^(*)H and^(*)FAL intermediates on the Pd surface for subsequent hydrogenation,experimentally confirming its high ECH activity and Faradaic efficiency.The free energies determined using DFT calculations indicated that^(*)H addition to the carbonyl of FAL on Pd{111}was thermodynamically preferred over desorption to gaseous H2,contributing to efficient ECH to afford FOL at the expense of H2 evolution.The obtained insights into the facet-dependent ECH underline that surface bindings assist ECH or H2 evolution considering their competitiveness.These findings are expected to deepen the fundamental understanding of electrochemical refinery and broaden the scope of electrocatalyst exploration.

Support Effects on Thiophene Hydrodesulfurization over Co-Mo-Ni/Al_2O_3 and Co-Mo-Ni/TiO_2-Al_2O_3 Catalysts

A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst （SC） had aromatic structure, composed of carbon enriched inner core, and oxygen-containing （SO3H, COOH, OH） groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts （strong-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five （HZSM-5）, sulfated zir-conia） in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.

Current efficiency improvement of Zn-Fe alloy electrodeposition by hydrogen inhibitor

In order to inhibit hydrogen evolution and enhance current efficiency of Zn-Fe alloy electrodeposition from alkaline zincate solution, hydrogen inhibitors composed of the sulfur group elements were optimized on the basis of atom structures analysis. The effects of hydrogen inhibitor on the current efficiency of Zn-Fe alloy electroplating and their electrochemical behaviors were studied. The results indicate that hydrogen inhibitor can increase the current efficiency of Zn-Fe alloy electroplating evidently, from 63.28% without hydrogen inhibitor up to 83.54% with a hydrogen inhibitor at a volume fraction of 2.0%, while it has a minor influence on that of pure Zn plating, which maintains at 80%. The optimum volume fraction of hydrogen inhibitor is 2.0%.

Hydrogen sorption properties of nanocrystalline Mg_2FeH_6-based complex and catalytic effect of TiO_2

The diversities of hydrogen sorption properties of Mg2FeH6-based complexes with and without TiO2 were investigated. Mg2FeH6-based complexes with and without TiO2 were synthesized respectively by reactive mechanical alloying,and hydrogen sorption properties of the complexes were examined by Sieverts-type apparatus. The results show that the sample without TiO2 releases 4.43 % (mass fraction) hydrogen in 1.5 ks at 653 K under 0.1 MPa H2 pressure and absorbs 90% of the total 4.43 % (mass fraction) hydrogen absorbed in 85 s at 623 K under 4.0 MPa H2 pressure. But for the sample with TiO2 addition under the same condition,it only needs 400 s to release all of the stored hydrogen and 60 s to absorb 90% of the total hydrogen absorbed. The activation energies for desorption process of the samples with and without TiO2 are determined to be 71.2 and 80.3 kJ/(mol.K),respectively. The improvement in hydrogen sorption rate and and reduction in activation energy can be attributed to the addition of TiO2.

Stark Effect Dependence on Hydrogenic Impurities in GaAs Parabolic Quantum-Well Wires

The ground-state and lowest excited-state binding energies of a hydrogenic impurity in GaAs parabolic quantum-well wires （Q WWs） subjected to external electric and magnetic fields are investigated using the finite-difference method within the quasi-one-dimensional effective potential model. We define an effective radius Pen of a cylindrical QWW, which can describe the strength of the lateral confinement. For the ground state, the position of the largest probability density of electron in x-y plane is located at a point, while for the lowest excited state, is located on a circularity whose radius is Pen. The point and circularity are pushed along the left haft of the center axis of the quantum-well wire by the electric field dire ted along the right half. When an impurity is located at the point or within the circularity, the ground-state or lowest excited-state binding energies are the largest; when the impurity is apart from the point or circularity, the ground-state or lowest excited-state binding energies start to decrease.

Understanding surface charge effects in electrocatalysis.Part 2:Hydrogen peroxide reactions at platinum

Electrocatalytic activity is influenced by the surface charge on the solid catalyst.Conventionally,our attention has been focused on how the surface charge shapes the electric potential and concentration of ionic reactant(s)in the local reaction zone.Taking H_(2)O_(2)redox reactions at Pt(111)as a model system,we reveal a peculiar surface charge effect using ab initio molecular dynamics simulations of electrified Pt(111)-water interfaces.In this scenario,the negative surface charge on Pt(111)repels the O-O bond of the reactant(H_(2)O_(2))farther away from the electrode surface.This leads to a higher activation barrier for breaking the O-O bond.Incorporating this microscopic mechanism into a microkinetic-double-layer model,we are able to semi-quantitatively interpret the pH-dependent activity of H_(2)O_(2)redox reactions at Pt(111),especially the anomalously suppressed activity of H_(2)O_(2)reduction with decreasing electrode potential.The relevance of the present surface charge effect is also examined in wider scenarios with different electrolyte cations,solution pHs,crystal facets of the catalyst,and model parameters.In contrast with previous mechanisms focusing on how surface charge influences the local reaction condition at a fixed reaction plane,the present work gives an example in which the location of the reaction plane is adjusted by the surface charge.

Proton irradiation effects on HVPE GaN

GaNs grown by hydride vapor phase epitaxy(HVPE) were irradiated by protons with different fluences.The changes of surface topography of as-grown and irradiated samples were characterized by atomic force microscopy(AFM).The crystal quality and optical properties of GaN films were examined by the variations of the micro-Raman and photoluminescence(PL) spectra with proton fluence.It was observed that the surface became a little more rough after irradiation.The Raman spectra indicated that the strain of materials and carrier concentration were not affected by the proton injection.The full-width at half-maximum(FWHM) of E 2 high phonon mode narrowed,which was consistent with the FWHM of PL near-band-edge emission(BE).The spectra of yellow luminescence and blue luminescence normalized to the intensity of BE demonstrated a little increase of Ga vacancy and a large decrease of O N,which may be the main reason for the change of optical properties.

Enzyme Activities in Perfluorooctanoic Acid (PFOA)-Polluted Soils

Perfluorooctanoic acid （PFOA） is a popular additive of the chemical industry; its effect on activities of important soil enzymes is not well understood. A laboratory incubation experiment was carried out to analyze the PFOA-induced changes in soil urease, catalase, and phosphatase activities. During the entire incubation period, the activities of the three soil enzymes generally declined with increasing PFOA concentration, following certain dose-response relationships. The values of EC10, the contaminant concentration at which the biological activity is inhibited by 10%, of PFOA for the soil enzyme activity calculated from the modeling equation of the respective dose-response curve suggested a sensitivity order of phosphatase 〉 catalase 〉 urease. The effect of PFOA on soil enzyme activities provided a basic understanding of the eco-toxicological effect of PFOA in the environment. Results of this study supported using soil ohosohatase as a convenient biomaxker for ecological risk assessment of PFOA-oolluted soils.