A new approach for the synthesis of K-free nickel hexacyanoferrate

A Ni, Al hydrotalcite-like compound (Htlc) has been proven an useful host material for an alternative synthesis of a K⁺-free mixed hexacyanoferrate Ni_1.5Fe^III(CN)₆, which is very difficult to obtain in bulk. The first stage of the procedure consists in the intercalation of hexacyanoferrate(III) inside the Htlc structure. The intercalated Htlc has been treated with a NiNO₃ solution. The obtained material has been characterized by XRD, XAS Raman and FT-IR spectroscopy. The voltammetric response of the compound obtained after the complete solubilization of the Htlc host shows a typical fingerprint of nickel hexacyanoferrate material with a very low level of potassium. Elemental analysis confirmed the absence of K⁺ and thus the occurrence of K⁺-free nickel hexacyanoferrate (14% yield).     

The Effect of Nb Loading on Catalytic Properties of Ni/Ce0.75Zr0.25O2 Catalyst for Methane Partial Oxidation

In this study,the effect of Nb loading on the catalytic activity of Ce_(0.75)Zr_(0.25)O_2-supported Ni catalysts was studied for methane partial oxidation.The catalysts were characterized by BET,H_2 chemisorption,XRD,TPR,TEM and tested for methane partial oxidation to syngas in the temperature range of 400-800℃at atmospheric pressure.The results showed that the activity of methane partial oxidation on the catalysts was apparently dependent on Nb loading.It seemed that the addition of Nb lowered the catalytic activity for methane partial oxidation and increased the extent of carbon deposition. This might be due to the strong interaction between NiO and Nb-modified support and reduction of surface oxygen reducibility.     

Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes

Gas‐phase C―C coupling reactions mediated by Ni (II) complexes were studied using a linear quadrupole ion trap mass spectrometer. Ternary nickel cationic carboxylate complexes, [(phen)Ni (OOCR¹)]⁺ (where phen = 1,10‐phenanthroline), were formed by electrospray ionization. Upon collision‐induced dissociation (CID), they extrude CO₂ forming the organometallic cation [(phen)Ni(R¹)]⁺, which undergoes gas‐phase ion‐molecule reactions (IMR) with acetate esters CH₃COOR² to yield the acetate complex [(phen)Ni (OOCCH₃)]⁺ and a C―C coupling product R¹‐R². These Ni(II)/phenanthroline‐mediated coupling reactions can be performed with a variety of carbon substituents R¹ and R² (sp³, sp², or aromatic), some of them functionalized. Reaction rates do not seem to be strongly dependent on the nature of the substituents, as sp³‐sp³ or sp²‐sp² coupling reactions proceed rapidly. Experimental results are supported by density functional theory calculations, which provide insights into the energetics associated with the C―C bond coupling step.     

Crystal Structures of [Ni(Phen)(i‐Bu2PS2)2] and [Ni(Phen)3](i‐Bu2PS2)2 Complexes and Interaction between Coordinated 1,10‐Phenanthroline Molecules

Single crystals of [Ni(Phen)(iBu₂PS₂)₂] (I) and [Ni(Phen)₃](iBu₂PS₂)₂ (III) compounds were grown, and their structures were determined by Xray diffraction analysis (CAD4 diffractometer, MoK radiation, 3336 F _hkl , R = 0.0373 for I and 2575 F _hkl for III). The crystals of complex I have a triclinic unit cell with the following parameters: a = 11.097(1) , b = 14.903(2) , c = 22.650(3); = 75.18(1)°, = 80.50(1)°, = 75.07(1)°, V = 3479.2(7)³, Z = 4, _calc = 1.255 g/cm³, and space group 1; the crystals of III have a monoclinic unit cell with the following parameters: a = 19.010(3), b = 15.481(1) , c = 17.940(3); = 97.58(1)°, V = 5233.5(12)³, Z = 4, _calc = 1.292 g/cm³, and space group C2/c. The structure of complex I is built from mononuclear molecules, and the structure of III, from [Ni(Phen)₃]²⁺ complex cations and i Bu₂PS₂ ^- outersphere anions. The NiN₂S₄ coordination polyhedra in the structure of I and NiN₆ in the structure of III are distorted octahedra. Based on structural data, the interaction between the coordinated Phen molecules of complexes I, [Ni(Phen)₂(iBu₂PS₂)](iBu₂PS₂) (II), and III is considered, as well as the packing modes of these complexes.     

碳化硼纳米线的制备和结构

以碳纳米管为模板，通过加热碳纳米管与硼粉的混合物，获得了笔直的硼碳纳米线.对纳米线的结构和成分进行研究，结果表明纳米线主要为B4C纳米线.在部分B4C纳米线的端部存在Ni颗粒，这些端部具有Ni颗粒的纳米线构成了纳米磁针.讨论了B4C纳米线的生长机制，B4C纳米线的生长主要为硼原子在碳纳米管中扩散并发生化学反应，使得碳纳米管晶格结构发生重组，形成B4C纳米线.反应后，硼原子部分取代了碳纳米管中碳原子，修补了碳纳米管中的晶格缺陷，获得了形态笔直的B4C纳米线.     

离子液体中电沉积制备钴纳米线阵列

Porous anodic alumina (PAA) was used as a template to prepare Co nanowires array from 1-ethyl-3-methylimidazolium chloride ionic liquid by direct current method. The surface morphology of porous anodic alumina template was observed by field emission-scanning tunneling microscopy (FE-SEM) before and after the electrodeposition of Co nanowires. The electrodeposition of Co nanowires was characterized by transmission electron microscopy (TEM) and X-ray powder diffraction (XRD). TEM results indicate that the Co nanowire surface is coarse and porous when aqueous solution was used as electrolyte， and the Co nanowire deposited from the ionic liquid is uniform and smooth. XRD results show that the electrodeposition of Co is a mixture of crystal and microcrystal phase.     

酞菁类化合物对MH/Ni电池性能的影响

针对MH/Ni电池充电过程中氧的产生和不恰当的消除方式带来的内压升高和热量聚集使电池总体性能衰减很快的问题, 提出采用降低化学催化氧还原的比例, 提高热量产生少的电催化氧还原比例的方法加以解决.金属酞菁类化合物是一种电催化氧还原剂.添加酞菁的MH/Ni电池与对比电池进行容量衰减、内压、大电流放电等特性比较, 其性能均有显著提高.     

甲烷在Ni表面及La薄膜上激活解离化学吸附

利用分子束技术改变甲烷的平动能E_k来研究E_k及其法向分量E_n对甲烷在Ni表面及La薄膜上激活解离吸附的影响。对CH_4/Ni及CH_4/La系统, 当甲烷的平动能E_k分别低于58.5 kJ·mol~(-1)及52.3 kJ·mol~(-1)时, 没观察到甲烷的解离吸附。当甲烷的平动能超过此阈值时, 即对CH_4/Ni系统, 当Ek=58.5增至63.8 kJ·mol~(-1)时, 初始沾着几率s_0由0至0.54线性增加; 对CH_4/La系统, 当E_k=52.3增至63.8 kJ·mol~(-1)时, S_0由0至0.49线性增加。这些结果表明, 两个系统的化学吸附是不经过前趋态的直接化学吸附。最后求出CH_4/Ni, CH_4/La系统的表观活化能分别为46.8 kJ·mol~(-1)和38.1 kJ·mol~(-1)。     

氧化物担载Ni（C5H5）2衍生催化剂的EXAFS表征

本文以二茂镍为母体化合物,以氧化铝和氧化硅为担体制备了担载镍催化剂。为了表征其结构特点,对这些催化剂热分解处理前后的样品在日本筑波高能物理研究所(Photon-Factory)的同步辐射加速器BL—10B EXAFS实验站进行了外延x-光精细结构谱测定(透射法)。以单散射球面波理论对实验结果进行了多参数拟合,同时对母体化合物也进行了平行测定和拟合,以验证数据及拟合方法的可靠性。研究结果表明,母体化合物的EXAFS结果与文献XRD相一致;母体化合物与担体表面发生了强烈的化学作用;镍组分在催化剂表面高度分散,氧化铝与Ni(C_5H_5)_2有更强的相互作用形成。Ni[(O)_s]_n(n≈4),近一半的镍原子周围有0.30 nm处的镍原子散射;氧化硅上除Ni[(CO)_s]_n(n≈3)外,在0.30 nm处有配位数为2的非成键Ni原子。     

EDS X-Ray Investigation of Interdiffusion in Au–Ni Micro- and Nanolayers

The interdiffusion process in thin and thick (500nm–60µm) Au–Ni layers deposited on different substrates is studied using the EDS technique. In-depth X-ray analysis based on the Pouchou and Pichoir method is applied for obtaining the concentration profiles in nanometre scale multi-layers. A theoretical analysis using the Darken method is employed for modelling interdiffusion in the Au–Ni system. Computer simulations, where intrinsic diffusivities of the Au and Ni are functions of composition, are presented and compared with experimental results.