Structure Studies on New Types of Macrocyclic Compounds Part V．Crystal Structure of Nickel（II） Complex of 5，12－Diphenyl－7，14－dimethyl－1，4，8，11－tetraazacyclotetradecane－N＇，N－diacetic Acid

Crystal structure of nickel（II） complex with a new 14 membered tetraazamacrocyclic ligand 5,12-diphenyl-7,14-dimethyl-1,4,8,11-tetraazacyclotetradecane-N’,N-diacetic acid,Ni[N4C10（CH2COO）2（C6H5）2]·2H2O, Mr= 589. 38 is reported.It crystallizes in monoclinic P21/c space group with a=12.949（6）,b=16.373（3）,c=14.232（16）,β=98.68（6）°,V=2982.9（7）,Z=4,Dc=1.312 gcm-3,μ=6.953 cm-1,F（000）=1256.0.Finally,the structure was refined to R=0.080,Rw=0.065 for 2952 reflections.The central nickel ion of the complex forms an octahedron with four nitrogen atoms of the macrocycle and two oxygen atoms of the appended carboxylate groups.Two phenyl planes of the ligand are almost parallel to each other.

In Situ Synthesis of Titanium Nickel Intermetallic Compounds Layer and TiN Coating By Laser Cladding

Laser cladding,together with laser nitriding was used to synthesize a titanium nickel intermetallic compound layer on the nickel substrate and a TiN coating on the cladding layer. During the laser cladding, Ti and Ni powders were blown into the melting pool by a six-hole coaxial nozzle powder injection system. Exothermic reactions between Ti and Ni took place in the melting pool, and a cladding layer of titanium nickel intermetallic compounds was produced. Laser nitriding in a nitrogen-rich atmosphere followed the production of the cladding layer, and formed a golden yellow TiN layer over it. An optical and a scanning electron microscope were used to investigate the microstructures and measure the thicknesses of the cladding layer and the TiN layer. Phase identification was carried out by XRD. For the nitriding sample, the microhardness profile of the clad layer was tested. The optimal process parameters of the in situ synthesis of titanium nickel intermetallic compounds were obtained.

镍基磷化物复合材料在催化电解水析氢性能提升方面的研究进展

镍基磷化合物因其自身的类氢化酶电子结构和其出色的稳定性被证明具有良好的电解水析氢能力。单金属磷化物因其本征活性不足、导电性不高及稳定性较差等问题,使其在实际应用上受到了限制。综述了结构新颖、性能优异和稳定性高的镍基磷化物复合材料的研究进展,总结和分析了通过杂原子掺杂、形貌调控、结合自支撑材料和复合新型材料(碳纳米管、石墨烯、石墨炔、二维材料MXene)等方式在调控催化材料的电子结构、微观形貌、促进长时间电解稳定性、增大比表面积和提高导电性方面提升电解水析氢性能的研究成果。为探索催化活性高和结构稳定兼备的新型镍基磷化物复合材料提供研究方向。

Abnormal Expression of Eukaryotic Translation Factors in Malignant Transformed Human Bronchial Epithelial Cells Induced by Crystalline Nickel Sulfide

Objective To study the oncogenic potential of mouse translation initiation factor 3 （TIF3） and elongation factor-1δ （TEF-1δ） in malignant transformed human bronchial epithelial cells induced by crystalline nickel sulfide （NiS）. Methods Abnormal expressions of human TIF3 and TEF-1δ genes in two kinds of NiS-transformed cells and NiS-tumorigenic cell lines were investigated and analyzed by the reverse transcript polymerase chain reaction （RT-PCR） and fluorescent quantitative polymerase chain reaction （FQ-PCR）, respectively. Results RT-PCR analysis primarily showed that both human TIF3 and TEF-1δ mRNA expressions in two kinds of NiS-transformed cells and NiS-tumorigenic cell lines were increased as compared with controls. FQ-PCR assay showed that the levels of TIF3 expressions in the transformed cells and tumorigenic cells were 3 and 4 times higher respectively, and the elevated expressions of TEF-16 eDNA copies were 2.7- to 3.5-fold in transformed cells and 4.1- to 5.2-fold in tumorigenic cells when compared with non-transformed cells, indicating that the over-expressions of human TIF3 and TEF-1δ genes were related to malignant degree of the cells induced by nickel. Conclusions These findings demonstrate that there are markedly abnormal expressions of TIF3 and TEF-1δ genes during malignant transformation of human bronchial epithelial cell lines induced by crystalline NiS. They seem to be the molecular mechanisms potentially responsible for human carcinogensis due to nickel.

NiCo-LDH材料的形貌分析与电化学性能研究

采用一步水热法在泡沫镍上合成镍钴层状双金属氢氧化物(NiCo-LDH)电极材料,用扫描电镜分析电极材料的微观形貌,X射线衍射仪分析电极材料的物相,并在不同扫描速率以及不同电流密度下NiCo-LDH纳米材料进行了电化学性能测试。结果表明:随着尿素含量的增加,NiCo-LDH的形貌由六角片状、草丛状,最后形成片层上带有针状形貌。扫描速率为10 mV·s^(-1)时,在CV曲线中可以清晰地看到氧化还原峰。电极在0.30~0.35V之间的充放电曲线出现对称的充放电平台,说明其充放电容量和充放电时间均较优,该复合材料的电容性能良好。

双金属钕镍有机框架化合物的制备及其电化学性能

[目的]稀土元素掺杂及双金属离子配位的金属有机框架化合物(MOFs)具有良好的电化学性能。[方法]以Nd、Ni元素为双金属离子源,均苯三甲酸(BTC)为有机配体,采用溶剂热法制备了具有棱柱状结构的双金属有机框架复合物材料(Nd Ni-MOFs)。采用循环伏安(CV)、恒电流充放电(GCD)和电化学阻抗谱(EIS)考察了Nd Ni-MOFs的电化学性能。[结果]NdNi-MOFs电极在1 A/g电流密度下的比电容可达1 280 F/g,而在8 A/g电流密度下循环充放电5 000次后的比电容为1 145 F/g,电容保持率达88.3%。由Nd Ni-MOFs电极组成的对称电容器在功率密度204.2 W/kg下的能量密度达到175 W·h/kg,充放电循环稳定性良好。[结论]Nd Ni-MOFs有望用作电容器、电池等的电极材料。

镍基镁渣催化剂对生物质焦油模化物催化重整特性实验研究

采用湿浸渍法制备Ni/γ-Al_(2)O_(3)和Ni/MS(magnesium slag)催化剂,选择糠醛、甲苯、萘、芘作为生物质焦油的模化物,研究不同镍基催化剂对四类焦油模化物在固定床反应器内进行催化重整的重整特性。结果表明,Ni/MS催化剂在催化所有模化物的重整反应时,气相碳转化率和气体产率均明显高于Ni/γ-Al_(2)O_(3)催化剂。当水分子物质的量与碳原子物质的量之比为1.5时,糠醛的气相碳转化率达到最高值86.54%。X射线衍射(XRD)结果表明,Ni/MS催化剂上存在的多种固溶体(NiO-Fe_(2)O_(3)、NiO-MgO)形成了多种活性位点。

湿法炼锌钴镍渣综合回收的试验研究

针对传统硫酸浸出湿法炼锌钴镍渣回收率低的情况,采用“酸洗-焙烧-选择性浸出”工艺进行处理。通过试验得到工艺的最佳条件:酸洗,L/S=3~4∶1、温度60~65℃、pH为1.5~2.0、反应时间0.5 h;焙烧,焙烧时间0.5 h;浸出,温度60~65℃、pH为4.5~5.0、L/S=3~4∶1、反应时间4 h。用该工艺对某钴镍3#渣进行处理,结果表明94%的锌可溶出,94%的钴、镍被富集在渣中,富集比为7。

NiFe-based nanostructures on nickel foam as highly efficiently electrocatalysts for oxygen and hydrogen evolution reactions

Water splitting,as an advanced energy conversion technology,consists of two half reactions,including oxygen evolution reaction(OER)and hydrogen evolution reaction(HER).However,the ideal electrocatalysts are noble metal based catalysts.Their high cost and scarcity in earth seriously restrict the large deployments.Ni Fe-based materials have attracted great attention in recent years due to their excellent catalytic properties for OER and HER.Nevertheless,their conductivity and electrochemical stability at high current density are unsatisfactory,resulting in ineffective water splitting due to high impedance and low stability.Recently,a series of catalysts coating Ni Fe-based materials on 3 D nickel foam were found to be extremely stable under the circumstance of high current density.In this review,we summarized the recent advances of NiFe-based materials on nickel foam for OER and HER,respectively,and further provided the perspectives for their future development.

Abrasive-assisted Nickel Electroforming Process with Moving Cathode

In traditional electroforming process for revolving parts with complex profiles, the drawbacks on surface of deposits, such as pinholes and nodules, will lead to varying physical and mechanical properties on different parts of electroformed components. To solve the problem, compositely moving cathode is employed in abrasive-assisted electroforming of revolving parts with complicated profiles. The cathode translates and rotates simultaneously to achieve uniform friction effect on deposits without drawbacks. The influences of current density and transla- tion speed on the microstructure and properties of the electroformed nickel layers are investigated. It is found that abrasive-assisted electroforming with compound cathode motion can effectively remove the pinholes and nodules, positively affect the crystal nucleation, and refine the grains of layer. The increase of current density will lead to coarse microstructure and lower micro hardness, from 325 HV down to 189 HV. While, faster translational linear speed produces better surface quality and higher micro hardness, from 236 HV up to 283 HV. The weld-ability of the electroformed layers are also studied through the metallurgical analysis of welded joints between nickel layer and 304 stainless steel. The electrodeposited nickel layer shows fine performance in welding. The novel compound motion of cathode promotes the mechanical properties and refines the microstructure of deposited layer.

Catalytic steam methane reforming enhanced by CO_2 capture on CaO based bi-functional compounds

Sorption enhanced steam methane reforming（SE-SMR） was performed to maximize hydrogen production and contemporary remove COfrom the product stream using bi-functional sorbent-catalyst compounds.Samples were tested at two different scales: micro and laboratory. The CaO amount varied in the CaO-CaAlOsorbent system synthesized by wet mixing(CaO content of 100 wt%, 56 wt%, 30 wt%, or 0 wt% and balance of CaAlO) which were upgraded to bi-functional compounds by impregnation of 3 wt% of Ni. Nitrogen adsorption（BET/BJH）, X-Ray Diffraction（XRD）, Temperature-Programmed Reduction（TPR） and Scanning and Transmission Electronic Microscopy（SEM and TEM, respectively） analyses were performed to characterize structural and textural properties and reducibility of the bi-functional materials and evaluate their catalytic behavior. A fixed sorbent composition CaO-CaAlO(56 wt% of CaO and CaAlObalance), was chosen to study the effect of different weight hourly space times（WHST） and CHstream compositions in SE-SMR activity. Impregnated mayenite at both micro and laboratory scales showed stable Hcontent of almost 74%, with CHconversion of 72% similarly to the values reported by the sample containing 30 wt% of CaO in the post-breakthrough.Sample with 30 wt% of CaO showed promisingly behavior, enhancing Hcontent up to almost 94.5%.When the sorption enhanced reaction is performed roughly 89% of CHconversion is achieved, and after the pre-breakthrough, the catalyst worked at the thermodynamic level. During cycling sorption/regeneration experiments, even if COremoval efficiency slightly decreases, CHconversion and Hyield remain stable.

STUDY ON THE SURFACE OF TITANIUM CARBIDE PARTICLE PACKAGED NICKEL

Two kinds of packaged processes by nickel on the surface of titanium carbide particle are studied in this work. One is the chemical nickel-plating, the other is the organometallic compound decomposition. The composition, structure and morphology of the packaged powder were analyzed with XRD, DAT/TGA, SEM, EPMA etc. It has been shown that nickel was even dispersed on the surface of titanium carbide particle by the. two kinds of processes, deposited nickel exists as spherical particles of about 0.1 μm in diameter. The merits and demerits of the two kinds of processes have been compared, the organometallic copmound decomposition among them is a kind of hopeful method, which is not used by other researchers.

Structure of Potassium of Undecatungstomononickelosilicate

The compound K4[α-SiNiW11O38]·10H2O,Mr=3053.86,crystallizes in the orthorhombic, space group Pnn2 with cell dimensions a=14.203（8）,b=14.214（6）,c=12.460（3）,V=2515（2）,Z=2,Dc=4.03 g/cm￣3,λ（MoKα）=0.71069,μ=273.1 cm（-1）,F（000）=2672.The structure was solved by direct methods.The least-square refinement based on 1190 observed reflections[I】 6σ（I）] converged to a final R=0.076.The anion in the title compound is of α type Keggin structure,although the octahedron MO6 is greatly distorted. Atoms Ni and W are statistically distributed in the crystal.

Synthesis and Characterizaion of a New Inorganic-organic Sulfate Compound——Crystal Structure of [Ni(H_2O)_6][H_2N(C_2H_4)_2NH_2](SO_4)_2

Ni(H_2O)_6][H_2N(C_2H_4)_2NH_2](SO_4)_2 is an inorganic-organic compound with a new open framework synthesized by hydrothermal method, and characterized by means of single-crystal diffraction and spectroscopic data. The compound crystallized in a monoclinic space group P2_1/n with a=1.29089(2) nm, b=1.06301(3) nm, c=1.33202(4) nm, β=114.0870(10)°, V=1.67127(8) nm 3, Z=4, and was solved by using the direct method and the least-squares refinement converged at R=0.0214[I>2σ(I)]. The structure consists of isolated Ni(H_2O)_6 octahedra and SO_4 tetrahedra, with both of them hydrogen-bonded to piperazine cations.

无定形NiCoSe电极的碱性电解水析氢性能

采用电沉积法在镍丝网上合成Ni、Co共掺杂的无定形硒化物NiCoSe作为析氢催化剂电极,利用扫描电镜、X射线衍射仪、透射电镜、X射线光电子能谱仪等观察和分析NiCoSe电极的形貌与结构,通过电化学实验测试电极的电催化析氢性能。结果表明,NiCoSe电极表面镶嵌着球形NiCoSe颗粒,无明显裂纹。NiCoSe化合物为无定形状态,能提供更多的低能垒空穴。适当比例的Ni、Co共掺杂可对Se的电子结构进行调控,使催化剂的电子结合能发生偏移,进而增强催化剂对H原子的吸附能力,使NiCoSe析氢催化剂电极具有较高的本征催化活性。在1 mol/L KOH溶液中10 mA/cm2电流密度下,NiCoSe阴极的过电位为83 mV,塔菲尔斜率为108.98 mV/dec,控制反应速率的步骤为催化剂对H原子的吸附过程。在60 h电解后电流密度衰减率小于5%。

医用NiTi细丝与304SUS细丝对焊研究进展

在介入医疗器械领域,镍钛合金细丝与不锈钢细丝是最常用的两种金属材料.镍钛丝具有优异的回弹性、柔软性,不锈钢丝具有优异的刚性和推送性能,将镍钛丝和不锈钢丝进行同轴焊接能显著提高产品的操控性.目前,大多采用的连接方式是胶水粘接、套管保护等方式,达不到理想的性能,超细丝径的镍钛丝与不锈钢丝的同轴焊接是研究的热点和难点.该文对镍钛丝与不锈钢丝焊接的关键问题进行了综述,总结相关焊接方法的最新研究进展,比较不同焊接方法的特点,重点讨论超细异种合金丝焊接过程的析出相及金属间化合物对焊接区域力学性能的影响.

催化生物质焦油模型化合物热解规律的研究

为进一步开发可再生能源,探究了生物质焦油的催化转化路径。试验以分子筛为载体制备了Ni基分子筛催化剂,对生物质焦油相关模型化合物进行催化热解研究,考察了不同催化剂以及热解温度的影响。结果表明,Ni的负载很大程度上提高了催化剂的催化活性,促进了催化反应向气体产物方向进行;随着助剂金属Ca,Co的二次负载,金属间的相互作用进一步提高了催化剂的机械强度和反应稳定性。通过对热解温度的研究,发现随着温度升高,模型物转化率和热解气产率显著提高,高温促进了催化剂与模型物间的氢转移反应。各模型化合物在Ni-CaCo/HZSM-5的催化作用下,均可以从大分子有机物转化为小分子气体,其转化率可以达到90%以上。研究旨在为进一步深入研究焦油的催化转化奠定基础。

镍离子对氨羧配位体系无氰镀镉工艺的影响

采用氨羧配位体系无氰镀液对30Cr Mn Si A钢电镀镉。镀液组成和工艺条件为:CdCl_(2)·2.5H_(2)O 40~50 g/L,NH_4Cl 180~220 g/L,氨三乙酸60~80 g/L,乙二胺四乙酸20~30 g/L,NiCl_(2)·6H_(2)O 50~300 mg/L(即Ni^(2+)12.3~74.1 mg/L), pH 6.5~7.5,室温,电流密度1 A/dm~2,时间15~25 min。通过阴极极化曲线测试、循环伏安分析和霍尔槽试验研究了Ni^(2+)质量浓度对镉电沉积行为和镀液均镀能力的影响,并通过光泽度测定、扫描电镜观察和塔菲尔曲线测量分析了Ni^(2+)质量浓度对Cd镀层外观、表面形貌和耐蚀性的影响。结果表明,镀液中添加适量Ni^(2+)可以在一定程度上改善Cd镀层的外观和耐蚀性,但对其他性能的影响不明显。Ni^(2+)不宜单独用作无氰镀镉的添加剂。

富镍三元层状正极材料表面残碱去除工艺:研究进展、挑战及展望

富镍LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)/LiNi_(1-x-y)Co_(x)Al_(y)O_(2)(NCA)三元层状正极材料因其比容量高、成本低等优势,被认为是最具前景的锂电池正极材料之一。但由于其对空气中H_(2)O和CO_(2)的敏感效应,表面易生成残碱化合物LiOH/Li_(2)CO_(3)(RLCs),而RLCs的存在会急剧恶化富镍三元材料热稳定性能和电化学性能,致使其大规模商业化应用面临严峻挑战。本文首先综述了RLCs的组成和形成机理,并系统概括RLCs引起的微裂纹扩展、Li^(+)/Ni^(2+)混排、界面副反应和晶格相变等材料失效机制以及常用RLCs去除策略;重点阐述去离子水洗涤、无水乙醇洗涤、溶液洗涤及后续一体化处理等三种RLCs去除工艺的研究进展及对材料结构、形貌及电化学性能的影响机理。最后,归纳总结上述溶液洗涤去除RLCs策略的特点,并对富镍NCM/NCA三元层状正极材料表面残碱去除工艺的未来研究方向进行展望。