Formation of CO(x)-free H2 and cup-stacked carbon nanotubes over nano-Ni dispersed single wall carbon nanohorns

Transitional metals (M) were dispersed on single-wall carbon nanohorns (M/SWCNHs, M = Fe, Co, Ni, Cu) by simple thermal treatment of the deposited metal nitrate without H(2) reduction. Nanometallic Ni particles on SWCNH were evidenced by high-resolution transmission electron microscopic observation and X-ray photoelectron spectroscopy. The nano-Ni dispersed on SWCNH showed the highest CH(4) decomposition activity; the activity of used transitional metals decreases in the order Ni ? Co > Fe ? Cu. On the other hand, the reaction rate over Ni/SWCNH was much larger than that over Ni/Al(2)O(3), and the former provided CO(x)-free H(2) and cup-stacked carbon nanotubes, while Ni/Al(2)O(3) produced CO(x) in addition to H(2). SWCNH was superior to Al(2)O(3) as the catalyst support of Ni for the CH(4) decomposition reaction.     

Characterization of magnetic nanoparticles using energy-selected transmission electron microscopy.

Fe, Co, and Ni magnetic nanoparticles have been characterized using energy-selected imaging in a high-resolution transmission electron microscope. The samples comprised Fe/FeO x and Co/CoO x nanoparticles synthesized by inert gas evaporation and a Ni/C nano-composite prepared by a sonochemical method. All of the particles examined were found to be between 5 and 30 nm in size, with the Fe and Co crystals coated in 5-10 nm of metal oxide layer and the Ni metallic crystallites embedded in an amorphous carbon spherical matrix.     

Thermal decomposition of bivalent transition metal malonates in various atmospheres

The thermal decomposition of the malonates of bivalent transition metals (Mn, Fe, Co, Ni, Cu and Zn) was investigated by mainly TG-DTA, X-ray diffraction analysis and evolved gas analysis in atmospheres of N₂, CO₂ and O₂ and in the air. It was shown that CO₂ has an inhibiting effect on the decomposition whereas O₂ and air have the accelerating effects on the basis of N₂. The decomposition of the salts investigated can be classified into three groups from solid decomposition products: Mn and Zn malonates gave the metal oxides including 1–1.5 moles of elementary carbon, while Cu and Ni malonates gave the metals with 1–1.5 moles of the carbon. Fe and Co malonates in the last group gave once the metal oxides with 1-0.5 moles of the carbon and the oxides produced were subsequently reduced to the metals by the carbon. A possible reaction mechanism for the malonates was discussed and compared with those of the corresponding oxalates and succinates.     

Enhanced high-temperature cycle performance of LiFePO4/carbon batteries by an ion-sieving metal coating on negative electrode

LiFePO₄/mesocarbon microbead (MCMB) cells of which the carbon electrodes were, respectively, coated with different metal layers were characterized for their charge/discharge cycle performance at 55 °C. The examined metals included Au, Cu, Fe, Ni, Co, and Ti, and the superficial layers were 30–50 nm in thickness and deposited by vacuum sputtering. It was found that the presence of a either Au or Cu layer remarkably reduces capacity fading, while the rest metals only accelerate fading. There was observed a consistent trend between the capacity fading rate and the amount of the soild-electrolyte-interphase (SEI) deposition; the faster the capacity fading, the greater amount of SEI materials appearing on the surface of cycled carbon electrode. Microscopic and composition analyses indicates that the superficial Au and Cu layers act as a sieve to collect the Fe ions that result form erosion of LiFePO₄ before they diffuse into the interior of the carbon electrode, and that the so-deposited Fe particles do not show the tendency to catalyze the SEI formation, as in contrast to those directly deposited on the carbon surfaces.     

Structural and catalytic properties of ultra-dispersed silver powders prepared by metal evaporation with high-power electron beam. 1. Structural properties

Summary Structural properties of ultra-dispersed silver powders synthesized via high-temperature electron-beam evaporation of silver in different gases (Ar, N₂, He) were studied with XRD, TEM, EDX and XRF. The formation of specific oxide-like species on the particle surface of an Ag(Ar) powder was found. It was shown that these particles can contain argon atoms.     

Fe, Co, Ni-聚合物-C复合催化剂的制备及对乙醇电催化氧化性能研究

采用模板聚合物与金属离子配位-碳粉负载-还原方法得到的纳米复合材料P-M-C (P为聚合物, M为Fe, Co, Ni金属纳米颗粒, C为碳粉XC72). 利用红外光谱(IR)对中间产物进行了表征, 结果表明所制物质为目标产物P; 透射电镜(TEM)结果表明Fe, Co, Ni纳米粒子粒径多数为20～30 nm, 部分在10 nm左右, 纳米粒子均匀地分散在聚合物P上; 扫描电镜的能谱(SEM-EDS)分析结果证实了Fe, Co, Ni三种元素的存在. 通过循环伏安和计时电流法研究表明, 碱性介质中P-M-C复合催化剂对乙醇电化学氧化具有高催化活性和稳定性; 反向高效液相色谱(HPLC)结果表明乙醇氧化后的产物部分为乙醛和乙酸的混合物.     

Nanocomposites based on opal matrices and iron subgroup metal nanoparticles

Three-dimensional nanocomposites based on ordered opal matrices (OMs) and metal nanoparticles were prepared by the reduction of salts and oxides of iron subgroup metals (M = Ni, Co, and Fe) and their binary and ternary mixtures with isopropanol in a supercritical state. The effect of the composition of the initial salts (nitrates or chlorides) on the phase composition of OM/M composites was determined. For a binary system of Ni and Co nitrates (1 : 1), the particles of a NiCo solid solution in a cubic modification were formed in an opal matrix after treatment in supercritical isopropanol. For the Ni-Fe and Co-Fe systems, the nanoparticles of solid solutions based on nickel or ??-, ??-cobalt metal and also oxides or an MFe₂O₄ phase with the spinel structure were formed in opal matrices with the use of iron trichloride. The nanoparticles of iron metal and Ni₃Fe, NiFe, and CoFe intermetallic compounds with regular distributions of metal atoms were detected for the first time in addition to spinel phases upon the reduction of composites with Fe, Ni-Fe, and Co-Fe nitrates with supercritical isopropanol. The reduction of composites obtained by the thermal treatment of a ternary mixture of nickel and cobalt nitrates and iron chloride in supercritical isopropanol led to the formation of solid solution nanoparticles based on Ni, Co, and Fe with an fcc structure and an oxide phase with the spinel structure in the voids of opal matrices. In the composite based on an opal matrix and a ternary system of Ni-Co-Fe nitrates (1 : 1 : 1), the complete reduction of spinel phases to the intermetallic phases of Ni₃Fe, NiFe, and CoFe was noted.     

Improved catalytic performance of nitrided Co–Ti and Fe–Ti catalysts for oxygen reduction as non-noble metal cathodes in acidic media

M–Ti/carbon black electrocatalysts (M: Mn, Fe, Co, Ni, Cu, Mo) were prepared by the polymerized complex (PC) method and subsequent nitridation under ammonia flow, and were investigated as cathodes for the oxygen reduction reaction (ORR) in 0.1 M H₂SO₄ aq. Among the metals investigated, Co and Fe gave high onset potentials of 0.86 and 0.87 V vs. RHE, respectively. In comparison with the Co-only catalyst, the Co–Ti catalyst showed higher current, reflecting high density of Co-related active sites. The presence of Ti was also essential for the electrode stability under severe acidic and oxidizing conditions.     

Pressure dependence of secondary ion emission from selected 3d, 4d, and 5d transition metals under N2O, NO, and NO2

The reactant gas pressure dependence of secondary ion emission from surfaces of polycrystalline Cr, Fe, Co, Mo, Rh, W, Re, and Ir under the action of N₂O, NO and NO₂ was observed by means of moderate dynamic SIMS. The mass spectra for constant reactant gas pressure indicate the existence of two different groups of transition metals showing either dissociative or partial molecular adsorption behavior. This is confirmed at least above some suitable reactant gas pressure. Besides some special details (Fe/NO; Co/NO) several of the relative secondary ion intensities vs. reactant gas pressure exhibit similar curvature as for O₂, thus indicating the NO_x gases to be modified sources of oxygen. At higher pressures molecular secondary ions with and without metal atoms come to be appreciable.     

Recycling process of spent battery modules in used hybrid electric vehicles using physical/chemical treatments

The physical treatment/chemical treatments for recycling of spent lithium-ion battery modules in used hybrid electric vehicles as cathodic active materials were performed. The result by physical treatment showed that over 95 % valuable metals such as Co, Li, Ni, and Mn were concentrated in 65-mesh during a grinding time 2 min, while just 2.7 % Al was concentrated from spent lithium-ion batteries which were completely electric discharged after 70 min. Through reductive leaching with H₂O₂ and H₂SO₄, leaching efficiency of valuable metals with 65-mesh powder was almost 99 % Co, Mn, Ni, and Li under the conditions of 2 M H₂SO₄, 5 vol% H₂O₂, 60 °C, 300 rpm, 50 g/500 mL, and 2 h. After removing some impurities such as Cu, Al, and Fe, the leaching solutions containing Co, Mn, Ni, and Li could be utilized for manufacturing the precursor of cathodic active material of Li-ion battery. The precursor was manufactured by co-precipitation from the filtrate after calibration of Co, Mn, and Ni concentration adding NaOH and NH₄OH under the conditions over pH 11, 30 °C, 150 rpm, and 24 h. To maintain the pH, 11 is most important level for making homogeneous spherical Co–Mn–Ni hydroxide.     

Pressure dependence of secondary ion emission from selected 3d, 4d, and 5d transition metals under N2O, NO, and NO2

The reactant gas pressure dependence of secondary ion emission from surfaces of polycrystalline Cr, Fe, Co, Mo, Rh, W, Re, and Ir under the action of N₂O, NO and NO₂ was observed by means of moderate dynamic SIMS. The mass spectra for constant reactant gas pressure indicate the existence of two different groups of transition metals showing either dissociative or partial molecular adsorption behavior. This is confirmed at least above some suitable reactant gas pressure. Besides some special details (Fe/NO; Co/NO) several of the relative secondary ion intensities vs. reactant gas pressure exhibit similar curvature as for O₂, thus indicating the NO_x gases to be modified sources of oxygen. At higher pressures molecular secondary ions with and without metal atoms come to be appreciable. Received: 28 May 1997 / Revised: 2 February 1998 / Accepted: 4 February 1998     

Solubility of ferrocyanides and ferricyanides in sodium pyrophosphate

1. Prussian blue and the ferrocyanides of Cu, Cd, Zn, Ni, Co, Mn, UO₂ are dissolved by sodium pyrophosphate. Na₄[Fe(CN)₆] and the water soluble double sodium pylophosphates of the afore mentioned metals are formed. 2. The Ferricyanides of Cu, Cd, Zn, Ni, Co, react with sodiun pyrophospate forming Na₃[Fe(CN)₆] and the water soluble sodium double pyrophosphates of the aforementioned metals.     

Low-temperature solution synthesis of the non-equilibrium ordered intermetallic compounds Au3Fe, Au3Co, and Au3Ni as nanocrystals

Alloys and intermetallic compounds of Au with the 3d transition metals Fe, Co, and Ni are nonequilibrium phases that have many useful potential applications as catalytic, magnetic, optic, and multifunctional magneto-optic materials. However, the atomically ordered Au-M (M = Fe, Co, Ni) intermetallics are particularly elusive from a synthetic standpoint. Here we report the low-temperature solution synthesis of the L12 (Cu3Au-type) intermetallic compounds Au3Fe, Au3Co, and Au3Ni using n-butyllithium as a reducing agent. Reaction pathway studies for the Au3Co system indicate that Au nucleates first, followed by Co incorporation to form the intermetallic. The nonequilibrium intermetallic nanocrystals have been characterized by powder XRD, TEM, EDS, selected area electron diffraction, and nanobeam electron diffraction, which collectively confirm the compositions and superlattice structures.     

铁、钴或镍助剂促进的 Ag/SiO2 催化剂上气相催化合成 3-甲基吲哚

 将铁、钴或镍促进的 Ag/SiO2 催化剂用于苯胺和 1,2-丙二醇气相催化合成 3-甲基吲哚的反应中, 并采用 X 射线衍射、H2-程序升温还原和热重分析等技术对催化剂进行了表征. 结果表明, 铁或镍助剂的加入有助于提高 Ag/SiO2 催化剂的选择性. 其中, 铁的加入能增强活性组分银与载体间相互作用, 大大促进了银在载体表面上的分散, 使催化剂的初活性显著提高. 而钴或镍的加入虽然能略微减少反应过程中 Ag/SiO2 催化剂表面的积炭, 但加剧了银在反应过程中的烧结, 导致催化剂稳定性下降.     

有序介孔碳负载Fe、Co、Ni纳米晶的软模板合成及其表征

报道了在有序介孔碳基体中一步合成负载Fe、Co、Ni纳米晶的方法. 以间二苯酚和甲醛为碳源, F127为模板剂, Fe、Co、Ni的硝酸盐为前驱体, 通过软模板组装路线在酸性条件下合成了负载型有序介孔碳复合材料. 采用X射线衍射(XRD)、透射电镜(TEM)和氮气吸附等手段对所合成材料进行了表征. 结果表明: 合成的材料具有类似于SBA-15的有序介孔结构, 有序介孔碳负载Fe、Co、Ni纳米晶复合材料的比表面积分别为586、626和698 m²·g^-1. XRD和TEM表征结果证实了金属物种以高分散纳米晶的形式分布在介孔碳基体中.     

Salt‐Free Reduction of Nonprecious Transition‐Metal Compounds: Generation of Amorphous Ni Nanoparticles for Catalytic C–C Bond Formation

A salt‐free procedure for the generation of a wide variety of metal(0) particles, including Fe, Co, Ni, and Cu, was achieved using 2,3,5,6‐tetramethyl‐1,4‐bis(trimethylsilyl)‐1,4‐diaza‐2,5‐cyclohexadiene ( 1 ), which reduced the corresponding metal precursors under mild conditions. Notably, Ni particles formed in situ from the treatment of Ni(acac)₂ (acac=acetylacetonate) with 1 in toluene exhibited significant catalytic activity for reductive C? C bond‐forming reactions of aryl halides in the presence of excess amounts of 1 . By examination of high‐magnification transmission electron microscopy images and electron diffraction patterns, we concluded that amorphous Ni nanoparticles (Ni aNPs) were essential for the high catalytic activity.     

Determination of silicon using electrothermal Zeeman atomic absorption spectrometry in presence of some transition metals as modifiers

The transition metals ions Cr(III), Mn(II), Fe(III), Co(II), Ni(II), and Zn(II) in addition to Ca(II) have been used as modifiers in the determination of silicon using electrothermal Zeeman atomic absorption spectrometry. Co(II) proved to be the best. Graphite tubes treated with zirconium, in the presence of Co(II) as a modifier, exhibit higher sensitivity by a factor of five than untreated tubes. The modifier concentration and ashing and atomization temperatures have been optimized. Also interference of different inorganic cations and anions was studied.     

Emission of secondary ions from 3d, 4d, and 5d transition metals under chloro-trifluoro-methane CClF3 as reactant gas

Surface interactions of CClF₃ with polycrystalline samples of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Rh, Pd, Ag, Ta, W, Re, Ir, and Pt were investigated by means of moderate dynamic SIMS. As observed with other reactant gases these transition metals in most cases appear to be discernible into “dissociative” and (partial) “molecular” adsorbents. Small signals of oxidic secondary ions which are detectable for residual gas conditions vanished under the action of CClF₃. However, due to strong polarization by either of the halogens, the emission of Me²⁺ ions is enhanced for Ti, V, and Nb.     

Study on the solid solubility of transition metals in high-purity silicon by instrumental neutron activation analysis and anticompton-spectrometry

The solid solubility of the 3d metals Cr, Mn, Fe, Co and Ni in high-purity silicon was studied by INAA and electron paramagnetic resonance techniques in the temperature range of ≊600°C–1250°C. The solubility increases with atomic number from Cr to Mn and more distinctly from Co to Ni. For Mn, Fe and Co the solubilities are nearly the same within the experimental errors. An enthalpy of formation (ΔH) of about 2.8 eV was determined for Cr, Mn, Fe and Co, whereas for Ni 1.7 eV was derived. Relatively large diffusion coefficients were estimated from the rather short times, in which saturation of the solid solution was reached. From these observations and from the results of the EPR measurements it is concluded that the 3d metals occupy predominantly interstitial sites in the silicon lattice in thermal equilibrium.     

Transition metal-doped carbon sphere as enhanced catalysts for oxygen reduction

Herein, carbon sphere (CS-T) were successfully prepared by pyrolyzation melamine formaldehyde resin. And then different transition metals (Fe, Co, Ni) were doped on carbon sphere (CS-M-900). The scanning electron microscopes and elemental mappings prove that the transition metal particles are uniformly doped on the carbon sphere. Meanwhile, the X-ray photoelectron spectrum prove that the transition metals are zero-valence. Furthermore, the electrochemical testings showed the CS-Co-900 had more positive onset potential (0.93 V), half-wave potential (0.84 V), and peak potential (0.81 V). Furthermore, the CS-Co-900 had lower charge transfer resistance (44 Ω) and smaller Tafel slope (65 mV/dec). Most importantly, the oxygen reduction reaction on the CS-Co-900 turned out to be a four electron procedure with excellent methanol tolerance. The improved electrochemical properties towards oxygen reduction reactions of carbon sphere via cobalt doping suggested a design strategy towards future high-performance electrochemical devices.