Fabrication of nickel hydroxide electrodes with open-ended hexagonal nanotube arrays for high capacitance supercapacitors

A nickel hydroxide electrode with open-ended hexagonal nanotube arrays, prepared by hydrolysis of nickel chloride in the presence of hexagonal ZnO nanorods, shows a very high capacitance of 1328 F g(-1) at a discharge current density of 1 A g(-1) due to the significantly improved ion transport.     

Synthesis of Nanoporous Ni‐Co Mixed Oxides by Thermal Decomposition of Metal‐Cyanide Coordination Polymers

A straightforward strategy to prepare nanoporous metal oxides with well‐defined shapes is highly desirable. Through thermal treatment and a proper selection of metal‐cyanide coordination polymers, nanoporous nickel‐cobalt mixed oxides with different shapes (i.e., flakes and cubes) can be easily prepared. Our nanoporous materials demonstrate high electrocatalytic activity for oxygen evolution reaction.     

Highly efficient Fe_xNi_(1-x)O_y/CP electrode prepared via simple soaking and heating treatments for electrocatalytic water oxidation

The oxygen evolution reaction(OER) is a key step in the overall water splitting process. Numerous electrocatalysts have been developed to lower the overpotential and accelerate the kinetics of the OER. In this work, a simple soaking and heating treatment was used to form a stable and efficient Fe_xNi_(1-x)O_y/CP electrode. The electrode combined nickel and iron oxides on a commercial carbon paper were used for electrocatalytic water oxidation. The best Fe_xNi_(1-x)O_y/CP electrode(Ni/Fe = 15/1) displayed a current density of 10 mA/cm~2 at a low overpotential of 290 mV in 0.1 M KOH solution with a Tafel slope of 52 mV/dec.A higher current density of ~50 mA/cm~2 at the same overpotential and a lower Tafel slope of 43 mV/dec was obtained for this electrode in 1.0 M KOH solution. Excellent durability of the Fe_xNi_(1-x)O_y/CP electrode in 1.0 M KOH solution was confirmed under a high current density of 136 mA/cm~2 at an overpotential of 340 mV.     

混合硝酸镍和醋酸镍制备的催化剂的特征和催化加氢抗硫性能

使用直接还原镍盐前体[Ni(NO_3)_2/γ-Al_2O_3, NiAc_2/γ-Al_2O_3或Ni (NO_3)_2-NiAc_2/γ-Al_2O_3]和镍氧化物前体的方法制备催化剂,研究了它们的 表面特征和甲苯加氢抗硫性能。还原镍盐得到的催化剂比还原其焙烧成的氧化物制 得的催化剂金属的还原和分散程度高。Ni(NO_3)_2-NiAc_2/γ-Al_2O_3分解得到的 氧化物前体的TPR在约415 ℃出现了较小数量的块状NiO的还原峰;而Ni(NO_3)_2- NiAc_2/γ-Al_2O_3的TPR中镍盐分解成氧化物时的耗氢量变小。用氢溢流的概念和 镍盐分解时的耗氢量可以将TPR的结果和金属的分散性关联起来。在镍盐前体催化 剂上甲苯的加氢具有较高的活性,而两种盐摩尔比为1：1时,盐前体催化剂反应活 性出现了一极大值,同时盐和氧化物前体催化剂都给出了抗硫性能的极大值。     

镍钴氢氧化物的制备及其电化学性能

采用化学共沉淀法成功制备了片状镍钴氢氧化物,并探究了不同镍钴物质的量比对样品形貌及电化学性能的影响。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱仪(XPS)及比表面积孔径分析仪(BET)对样品的结构、形貌进行了表征,并利用循环伏安法、恒电流充放电法等对其电化学性能进行了分析。结果表明,n(Ni)∶n(Co)=4∶1的样品直接用作电极材料时,具有最好的电化学性能:在0.5 A/g的电流密度下拥有1852 F/g的高比容量;电流密度增大20倍时,仍拥有1330 F/g的高比容量。以镍钴氢氧化物为正极,活性炭为负极组装的非对称式超级电容器在346 W/kg的功率密度下,能量密度达52 Wh/kg,在循环10000圈之后电容保持率为92%。优异的电化学性能表明,片状镍钴氢氧化物是很有应用潜力的电极材料之一。     

Aldol condensation of furfural and acetone on layered double hydroxides

The Aldol condensation of furfural (Fur) with acetone (Ac) to 4-(2-Furyl)-3-buten-2-one (FAc) is one of the most important processes in the aqueous-reforming of oxygen-containing biomass derivatives and has been carried out in the presence of solid-base catalysts, calcined-rehydrated Layered Double Hydroxides (LDH). The Mg-Al Layered Double Hydroxides has been prepared by the coprecipitation, calcination and regeneration from mixed oxides by rehydration. The catalyst prepared with different Mg/Al molar ratios showed different catalytic performance and the best catalyst was with the Mg/Al molar ratio of 2.5. Phenol adsorption showed that the best catalyst had the largest numbers of accessible basic sites. The appropriate rehydration temperature and time for mixed oxides obtained by calcination were also investigated. The Mg-Al LDH catalysts can be regenerated by calcination at 773 K and rehydration in decarbonate water, but the regeneration is complex and incomplete. In addition, the catalyst calcined at high temperature also had activity, which was attributed to the formation of the Mg-Al spinels.     

Ordered mesoporous alumina-supported metal oxides

The one-pot synthesis of alumina-supported metal oxides via self-assembly of a metal precursor and aluminum isopropoxide in the presence of triblock copolymer (as a structure directing agent) is described in detail for nickel oxide. The resulting mesoporous mixed metal oxides possess p6 mm hexagonal symmetry, well-developed mesoporosity, relatively high BET surface area, large pore widths, and crystalline pore walls. In comparison to pure alumina, nickel aluminum oxide samples exhibited larger mesopores and improved thermal stability. Also, long-range ordering of the aforementioned samples was observed for nickel molar percentages as high as 20%. The generality of the recipe used for the synthesis of mesoporous nickel aluminum oxide was demonstrated by preparation of other alumina-supported metal oxides such as MgO, CaO, TiO 2, and Cr 2O 3. This method represents an important step toward the facile and reproducible synthesis of ordered mesoporous alumina-supported materials for various applications where large and accessible pores with high loading of catalytically active metal oxides are needed.     

Phase-selective synthesis of nickel phosphide in high-boiling solvent for all-solid-state lithium secondary batteries

Nickel phosphide particles were synthesized by thermal decomposition of a nickel precursor in a mixed solution of trioctylphosphine and trioctylphosphine oxide. The crystal phase and morphology of samples prepared by changing the solvents, the amount of trioctylphosphine as a phosphorus source, the reaction temperature, and the nickel precursor were characterized using X-ray diffraction and transmission electron microscopy. Spherical Ni(5)P(4) particles with diameters of 500 nm were obtained using nickel acetylacetonate as a nickel precursor at 360 °C for 1 h in trioctylphosphine oxide. NiP(2) particles with diameters of 200-500 nm were obtained using nickel acetate tetrahydrate at 360 °C for 5 h in trioctylphosphine oxide. All-solid-state cells were fabricated using NiP(2) particles as an active material and 80Li(2)S·20P(2)S(5) (mol %) glass-ceramic as a solid electrolyte. The Li-In/80Li(2)S·20P(2)S(5)/NiP(2) cell exhibited an initial discharge capacity of 1100 mAh g(-1) at a current density of 0.13 mA cm(-2) and retained a discharge capacity of 750 mAh g(-1) after 10 cycles.     

NiO/LaMnO3催化剂用于乙醇水蒸气重整反应

采用柠檬酸络合-浸渍法制备了NiO/LaMnO3钙钛矿型复合氧化物催化剂并将其应用于乙醇水蒸汽重整制氢反应, 考察了NiO含量、焙烧温度对催化剂性能的影响, 采用XRD、TPR和热分析等手段对催化剂进行了表征. 结果表明, 该催化剂具有高活性、高选择性和良好的稳定性. 催化剂中的NiO含量和焙烧温度对催化性能有显著影响. 在原料气体积组成为20%(体积分数, φ) C2H5OH 和水以及80%(φ)N2, 其中水醇摩尔比为3:1, 空速为80000 mL·h-1·g-1 cat, 反应温度为400 ℃时, 15%(质量分数, w)的NiO/LaMnO3上, 乙醇转化率接近100%. 关联催化剂活性和TPR及XRD实验结果, 发现催化剂的高活性源于由催化剂前驱体中进入钙钛矿型复合氧化物晶格中的镍离子被还原所得的金属镍.     

铜锆复合氧化物的结构对其催化选 择还原－氧化氮性 能的影响

用浸渍法和共沉淀法分别制得CuO---ZrO~2复合氧化具物有不同的选择还原NO~x的催化性能,采用XRD,BET,EXAFS和H~2---TPR等手段对样品进行了表征,发现浸渍法制备的样品具有的比表面较大,氧化锆被稳定在四方相。EXAFS实验表明,浸渍法制得样品的铜离子填入氧化锆表面空穴中,并以Cu^2+形式存在;500℃焙条件下用共沉淀法引入的铜离子可部分取代锆离子,在氧化锆体相高度分散形成均匀的无定形固溶体,铜离子在氧化锆体相的高度分散是形成表面弧立铜物种的关键。溶入氧化锆体相的铜离子在取代部位由于局部负电荷而使氧化性降低,是共沉淀法制备样品具有较高催化活性的主要原因。     

La~2NiO~4催化制备纳米碳管

制备了四方结构复合氧化物La~2NiO~4,并以其为催化剂前体,甲烷和一氧化碳为碳,合成出大量高纯度的纳米碳管。XRD结果表明La~2NiO~4经还原后,在La~2O~3的隔离作用下Ni晶粒实现纳米级均匀分散。利用TEM,HRTEM,SEM,XRD,Raman等手段对所制备的纳米碳管进行了观察和表征。所制备的纳米碳管管径均匀、石墨化程度较高,该法制备纳米碳管工艺简单、产量较高,产品易于纯化。     

Enhanced Electrochemical Capacitive Properties of Nickel‐Cobalt Oxide Nano‐flakes Materials

Nickel‐cobalt oxide nano‐flakes materials are successfully synthesized by a facile chemical co‐precipitation method followed by a simple calcination process. The studies show that the as‐prepared nickel‐cobalt oxides with different Ni/Co ratio are composed of NiO and Co₃O₄ compounds. The Co_0.56Ni_0.44 oxide material, which exhibits a mesoporous structure with a narrow distribution of pore size from 2 to 7 nm, possesses markedly enhanced charge‐discharge properties at high current density compared with the pure NiO and pure Co₃O₄. The Co_0.56Ni_0.44 oxide electrode shows a specific capacitance value of 1227 F/g at 5 mA/cm², which is nearly three times greater than that of the pure NiO electrode at the same current density.     

氟修饰的含Ni类水滑石在甲烷部分氧化制合成气中的应用研究

通过共沉淀法合成了含Ni/Mg/Al的类水滑石,并利用水滑石的"重构性能"将F^-引入到水滑石层间。焙烧该类水滑石后得到Ni/Mg/Al/O-F催化剂,采用XRD、SEM、CO₂-TPD、H₂-TPR、N₂吸附-脱附等手段对其结构进行了表征。结果表明,焙烧后的催化剂为方镁石结构,并具有丰富的介孔,Ni/Mg/Al/O-F较之不含F^-的复合氧化物Ni/Mg/AlO具有更小的比表面积、颗粒粒径和结晶度,但是碱密度明显增大,并且在甲烷部分氧化(POM)反应中表现出更高的活性和稳定性,反应120h后,活性没有下降。这是因为F^-的引入提高了催化剂碱性和活性组分Ni的分散,从而改善了催化剂的抗积炭和烧结能力。     

Vanadium-based Mixed Oxides Prepared from Thermal Decomposition of Citratorvanadium(IV) Precursor

Citrate method is broadly used for the preparation of mixed oxides and their highly dispersive pure phases^[1]. Up to now, most of the mixed oxides are prepared from putting the related chemical compounds together and sintering the mixture at high temperature, while the complexes formed during this process are uncertain. This will limit the design of high dispersibility and the purities of the resulted mixed oxides. Vanadium-based oxides are catalysts used in the partial oxidation of propane and butane. It has been demonstrated previously that the vanadium citrate complex with well-defined composition and structure is the better precursors for the preparation of V-based mixed oxide^[2], Using the precursor of barium dimeric(citrato) oxovanadium(IV) tetrahydrates Ba₂[VO(cit)]₂·4H₂O, barium pyrovanadate may be prepared with pre-determinated compositions and higher purities from thermal decomposition of the well-defined complexes at lower temperature.     

一些过渡金属多元氧化物陶瓷颜料的结构与光谱研究

由偏钛酸与钴、镍和锌的盐或氧化物在高温下煅烧合成11个不同颜色的多元氧化物。X-射线粉末衍射数据表明所有样品的结构:组分NiO摩尔数不超过TiO_2的样品是反式尖晶石型晶体,反之,样品是混合晶体。紫外-可见吸收-反射谱图表明10-11号样品同其他的比较具有变窄了的和高的反射峰。这样,它们可以作为绿色的陶瓷颜料。并探讨结构和光谱随组分而改变的原因。     

Amperometric nonenzymatic determination of glucose based on a glassy carbon electrode modified with nickel(II) oxides and graphene

We have developed a stable and sensitive nonenzymatic glucose sensor by modifying a glassy carbon electrode (GCE) with a composite incorporating nickel(II) oxides and reduced graphene. The oxides were generated by directly electrodepositing nickel on the GCE with a graphene modifier using a multi-potential pulse process, and then oxidizing nickel to nickel(II) oxides by potential cycling. In comparison to the conventional nickel(II) oxides-modified GCE, this new nickel(II) oxides-graphene modified GCE (NiO-GR/GCE) has an about 1.5 times larger current response toward the nonenzymatic oxidation of glucose in alkaline media. The response to glucose is linear in the 20 μM to 4.5 mM concentration range. The limit of detection is 5 μM (at a S/N of 3), and the response time is very short (<3 s). Other beneficial features include selectivity, reproducibility and stability. A comparison was performed on the determination of glucose in commercial red wines by high-performance liquid chromatography (HPLC) and revealed the promising aspects of this sensor with respect to the determination of glucose in real samples.

Development and optimization of magnetic technologies based processes for removal of some toxic heavy metals

In the developing countries where the cost is often a decisive factor, extensive studies were undertaken to test the most effective factors on the preparation, optimization and validation of the magnetic particles (or, more accurately, magnetizable particles) for removal of heavy metals from wastewaters. The objective of the proposed work was focused to provide promising solid-phase materials, which, are relatively in expensive and combine high surface capacity with fast efficient treatment. Four various metal oxides including hydrous ferric oxide (HFO), hydrous stannic oxide (HSO) and mixed ferric/stannic oxide (HMO), were prepared by precipitation with ammonia from metal chloride solutions. Two mixed oxides were prepared with different Sn/Fe ratios of 50% and 20%. Optimal conditions for the activation of these particles and the subsequent mixing of various metals oxides are tested together with the utility of the method to get a new composite material with developed chemical characteristics over their individual metal oxides. Factors affecting the sorption behavior of the prepared samples in basic and acid media were elucidated. The magnetic treatment procedure using the mixed oxide (50%) enables the equilibration step to be carried out rapidly mainly due to ferric oxide during the magnetization process and efficiently due to high capacity of the stannic oxide. A key factor in achieving very high uptake percentage is the reduction of non-specific binding of various heavy metals to the solid phase support. This is usually achieved by increasing the ion exchange capability, in addition to their adsorption process.     

New NixMg6−xMnO8 Mixed Oxides as Active Materials for the Negative Electrode of Lithium-Ion Cells

New mixed oxides with an Ni_xMg_6−xMnO₈ (x=0, 2, 4, 5 and 6) stoichiometry and NaCl-related structure have been prepared by heating mixed oxalate precursors at 600°C. The existence of a solid solution was confirmed by the decrease of the cubic unit-cell parameter when magnesium was substituted by nickel. The solids were used as electrode materials in lithium cells, which were potentiostatically cycled. The structural transformations during reaction with lithium have been studied by ex-situ X-ray diffraction. A maximum value of ca. 20 F mol⁻¹ is found during the first discharge of Ni₆MnO₈ electrodes. Annealing the non-crystalline discharged electrodes at 600°C allows to detect metallic nickel. While Ni₅MgMnO₈ improves capacity retention as compared with pure nickel, the extended substitution of nickel by magnesium leads to a progressive decrease in cell capacity. The reversible capacity values of ≤640 mA h g⁻¹ are explained in terms of the formation of Ni oxide that reacts with lithium reversibly. The potential in which the cell current peaks occur decreases on increasing the Mg content.     

Concentrated Ionic Fluids: Is There a Difference Between Chloride-Based Brines and Deep Eutectic Solvents?

Deep Eutectic Solvents (DESs) have been lauded as novel solvents, but is there really a difference between them and concentrated aqueous brines? They provide a method of adjusting the activity of water and chloride ions which can affect mass transport, speciation and reactivity. This study proposes a continuum of properties across concentrated ionic fluids and uses metal processing as an example. Charge transport is shown to be governed by fluidity and there is no discontinuity between molar conductivity and fluidity irrespective of cation, charge density or ionic radius. Diffusion coefficients of iron(III) and copper(II) chloride in numerous concentrated ionic fluids show the same linear correlation between diffusion coefficient and fluidity. These oxidising agents were used to etch copper, silver and nickel and while the etching rate increased with fluidity for copper, etching of silver and nickel only occurred at high chloride and low water activity as passivation occurred when water activity increased. Overall, brines provide a high chloride content at a lower viscosity than DESs, but unlike DESs, brines are unable to prevent passivation due to their high water content. The results show how selective etching of mixed metal waste streams can be achieved by tuning chloride and water activity.     

Nickel Hydroxide Supercapacitor with a Theoretical Capacitance and High Rate Capability Based on Hollow Dendritic 3D‐Nickel Current Collectors

A straightforward way to attain the theoretical capacitance and high rate capability of nickel hydroxide supercapacitors, by utilizing a mesoporous hollow dendritic three‐dimensional‐nickel (3D‐Ni) current collector is proposed. A facile electrodeposition method employing a hydrogen bubble template was chosen for rapid fabrication of the dendritic 3D‐nickel structure. After nickel hydroxide was deposited on the hollow 3D‐nickel current collector, it exhibited a highest capacitance of 3637 F g⁻¹ at a current density of 1 A g⁻¹, and retained 97 % of capacitance at a high current density of 100 A g⁻¹ with a cycle stability of over 80 % after 10 000 cycles. The enhanced performance could be attributed to the large surface area and high conductivity of the moss‐like dendritic 3D‐Ni current collector, which allowed direct contact between the active materials and the current collector, and reduced diffusion resistance between the surface of the active materials and the electrolyte. These results not only confirmed a facile fabrication method for high‐performance 3D metal nanostructures, but also offer a promising solution for state‐of‐the‐art energy storage systems.