铜修饰多孔镍自支撑电极的构建及其葡萄糖氧化性能

采用水热合成法制备了正八面体Cu₂O/Cu修饰的多孔Ni(NF)自支撑电极(Cu₂O/Cu-NF),并对其进行了形貌和结构表征。 在三电极体系下,在碱性介质中以循环伏安法和恒电位安培法测试其对葡萄糖催化氧化性能。 结果表明,150 ℃水热法制备的自支撑电极对葡萄糖的电催化氧化活性最强。 响应电流与葡萄糖浓度在3.7×10^-3~1.1 mmol/L和1.4~5.0 mmol/L范围内呈线性相关,响应灵敏度分别是6929和706.1 μA/(mmol·L^-1·cm²),且具有良好的选择性和稳定性,对无酶葡萄糖传感器的发展有重要意义。     

Fabrication of Acid Violet 34/Nickel Hydroxide Ultrathin Film and Its Electrocatalytic Performance for Glucose

This article reports the fabrication of Acid Violet 34 (AV34)/nickel hydroxide nanosheets ultrathin film on the glassy carbon electrode (GCE) via the electrostatic layer‐by‐layer (LBL) technique, and its electrocatalytic oxidation for glucose was demonstrated. UV‐vis absorption and electrochemical impedance spectra indicate the uniform deposition of the LBL film, with a continuous and smooth film surface observed by SEM and AFM. The electrochemical performance of the ultrathin film was studied by cyclic voltammetry and chronoamperometry. The (AV34/Ni(OH)₂)₅ ultrathin film modified electrode displays a fast direct electron transfer attributed to the Ni²⁺/Ni³⁺ redox couple as well as remarkable electrocatalytic activity towards the oxidation of glucose. The linear response was obtained in the range 0.5–13.5 mM (R=0.9994) with a low detection limit (14 µM), high sensitivity (25.9 µA mM^?1 cm^?2), rapid response (less than 1 s) and excellent anti‐interference properties to the species including ascorbic acid (AA), uric acid (UA), acetamidophenol (AP) and structurally related sugars. Therefore, the AV34/Ni(OH)₂ ultrathin film can be potentially used as a feasible electrochemical sensor for the determination of glucose.     

Hydrogenation of Glucose to Sorbitol by Using Nickel Hydroxyapatite Catalyst

A series of nickel hydroxyapatite catalysts were synthesized by the co-precipitation method followed by calcination and reduction. These catalysts were employed for the aqueous phase hydrogenation of glucose to sorbitol. The Ni-HAP catalyst with comparatively high surface area and acid-base strength gave high sorbitol selectivity in 1 h. Ni-HAP-4 catalyst with moderate Ni (3.5 wt. %) content having smaller and highly dispersed nickel particles gives an excellent yield of sorbitol, 97 % in 1 h. The Ni-HAP-4 catalyst works well with other polar protic solvents. Different characterization techniques like XRD, TEM, SEM-EDS, BET, NH₃-TPD, and CO₂-TPD were employed to analyze the Ni-HAP-4 catalyst.     

含有晶种的母液在氢氧化镍制备中的循环使用

ni(oh)2;制备;晶种;母液;循环使用     

Hydrothermal Synthesis of Titanium‐Supported Nickel Nanoflakes for Electrochemical Oxidation of Glucose

Titanium‐supported nanoscale flaky nickel electrode (nanoNi/Ti) was prepared by a hydrothermal process using hydrazine hydrate as a reduction agent. Its electrocatalytic activity as an electrocatalyst for the electrooxidation of glucose was evaluated in alkaline solutions using cyclic voltammetry (CV), chronoamperometric responses (CA) and electrochemical impedance spectra (EIS). The nanoNi/Ti electrode exhibits significantly high current density of glucose oxidation. A high catalytic rate constant of 1.67×10⁶ cm³ mol^?1 s^?1 was calculated from amperometric responses on the nanoNi/Ti electrode. Low charge transfer resistances on the nanoNi/Ti in 0.5 M NaOH containing various concentrations of glucose were obtained according to the analysis for EIS. Furthermore, amperometric data show a linear dependence of the current density for glucose oxidation upon glucose concentration in the range of 0.05–0.6 mM with a sensitivity of 7.32 mA cm^?2 mM^?1. A detection limit of 0.0012 mM (1.2 μM) M glucose was found. Results show that the prepared nanoNi/Ti electrode presents high electrocatalytic activity for glucose oxidation.     

磷钼酸修饰铂电极的电化学行为及对甲醇氧化的电催化作用

通过循环伏安扫描法制备了PMo₁₂修饰Pt/Pt电极,并研究了该修饰电极在硫酸溶液中的电化学行为。研究结果表明:虽然磷钼酸具有较大的分子尺寸,但在Pt/Pt电极上仍能发生吸附作用,并且由于PMo₁₂在电极上的吸附,降低了Pt/Pt电极上氢区和氧区的荷电量,另外在0.02V左右还观察到磷钼酸的氧化-还原峰。通过稳态极化曲线和循环伏安曲线研究了PMo₁₂修饰Pt/Pt电极对甲醇氧化的电催化作用。测试结果表明:PMo₁₂修饰铂基电极不但对甲醇的电氧化具有较高的活性,而且还有一定的抗CO中毒性。该修饰电极还具有较高的稳定性。     

降低Ni(OH)2中SO42-含量的实验研究

以NiSO4和NaOH为原料,采用控制溶液结晶法制备球形β-Ni(OH)2的过程中,通过加入添加剂降低了Ni(OH)2中SO4-2含量.考察了pH值、Ni2 浓度、NiSO4溶液流速、碱浓度、搅拌强度等因素对Ni(OH)2中SO42-含量的影响.     

掺锰氢氧化镍的结构与电化学性能

采用化学共沉淀法制备了锰取代的氢氧化镍样品，应用XRD技术对不同锰含量样品的相结构进行了表征，并用恒电流充放电、电流脉冲弛豫法和电化学阻抗技术研究了样品的电化学行为. XRD结果显示：锰含量少于20％时，样品主要由β相组成；而当锰含量达到28.3%时，可以得到具有纯α相结构的样品. 电化学研究结果表明：掺锰的氢氧化镍样品具有优良的电化学循环稳定性；锰的掺杂提高了氢氧化镍电极的析氧电位，增大了样品的质子扩散系数； 具有较低锰含量的氢氧化镍样品显示了较大的放电容量和较高的放电电位.     

Transport of alkaline cation and neutral species through the α-Ni(OH)2/γ-NiOOH film electrode

The transport of alkaline cation and neutral species through the α-Ni(OH)₂/γ-NiOOH film electrode has been investigated during the hydrogen extraction from and injection into the film electrode in 0.1 M LiOH, KOH and CsOH solutions by using the electrochemical quartz crystal microbalance technique combined with the potentiostatic current transient technique and cyclic voltammetry. From the ohmic relationship between the initial current density and the applied potential step, it is suggested that the hydrogen transport through the film electrode is exclusively governed by "cell-impedance". On the basis of the "cell-impedance-controlled" hydrogen transport, the mass change measured indicates that during the hydrogen extraction, the alkaline cation is slowly inserted into the film electrode before the finish of the current plateau. After the period of current plateau has finished, it is drastically inserted at an exponential rate. By contrast, during the hydrogen injection, the extraction of alkaline cation is nearly completed before the finish of the current plateau. Most of the neutral species are incorporated into the film electrode during the immersion prior to the hydrogen extraction. The minority is not incorporated until the finish of the current plateau during the hydrogen injection. Electronic Publication     

Glucose Electro‐oxidation on Graphite Electrode Modified with Nickel/Chromium Nanoparticles

In this study, an available and inexpensive graphite substrate, was easily modified with Ni/Cr nanoparticles via electrodeposition technique in a very short time (3 min) and used as an electrocatalyst for glucose oxidation in alkaline solution. Graphite electrode modified with Ni/Cr nanoparticles demonstrated an outstanding electrocatalytic performance to glucose oxidation in comparison to examined Ni‐based electrodes or even different materials in other reports. It is noteworthy to mention that adding a little Cr led to a synergistic effect with Ni; accordingly, the presence of Cr not only resulted in a greater adsorption of glucose molecules by chromium oxide but also boosted conductivity of the nickel oxide because of the enhancement of Ni(III) amount. The electrochemical studies were performed by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The morphology and structure of catalyst layer was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD) and energy dispersive x‐ray spectroscopy (EDS). The linear range of the electrode by cyclic voltammetry was between 2–31 mM with a high sensitivity of 2094 μA cm^?2 mM^?1. The repeatability and reproducibility of the proposed electrode was examined in glucose solution which were 0.3 % and 4.7 %, respectively. According to the low cost, ease and fast preparation, good repeatability and high sensitivity, this electrode can be a good candidate for nonenzymatic glucose oxidation.     

Photoelectrochemical‐assisted Batch Injection Analysis (PEC‐BIA) of Glucose Exploiting Visible LED Light as an Excitation Source

This work describes the development of a novel method for glucose determination exploiting a photoelectrochemical‐assisted batch injection analysis cell designed and constructed with the aid of 3D printer technology. The PEC‐BIA cell was coupled to a LED lamp in order to control the incidence of light on the Cu₂O/Ni(OH)₂/FTO photoelectroactive platform. The electrochemical characteristics of Cu₂O/Ni(OH)₂/FTO photoelectroactive platform were evaluated by cyclic voltammetry, amperometry, and electrochemical impedance spectroscopy. The PEC‐BIA cell presented linear response range, limit of detection based on a signal‐to‐noise ratio of three, and sensitivity of 1–1000 μmol L^?1, 0.76 μmol L^?1 and 0.578 μA L μmol^?1, respectively. The PEC‐BIA method presented a mean value of the recovery values of 97.0 % to 102.0 % when it was applied to glucose determination in artificial blood plasma samples which indicates the promising performance of the proposed system to determine glucose.     

洗涤时pH值对纳米级β-Ni(OH)2的团聚程度和电化学性能的影响（英文）

Nano-scale nickel hydroxide was prepared by precipitate transformation method in the paper. Effect of rinse pH on the agglomeration degree and electrochemical performance of nano-scale Ni (OH)2 was investigated. The measurement results of XRD and TEM indicate that the prepared nano-scale Ni (OH)2 is β (II)-phase, the grain size is in the rang of 10 ～ 50nm, and rinse pH exerts a great influence on the agglomeration degree of nano-scale Ni(OH) 2.The agglomeration of material becomes very obvious when rinse pH = 11, and the density of nano-scale Ni(OH)2 is enhanced obviously. Cyclic voltammetry(CV) and simulate cells experiment show that nano-scale Ni(OH)2 with suitable agglomeration degree have better electrochemical CV performance than those with ideal disperse Ni (OH)2and micron Ni(OH)2, and its proton diffusion coefficient is also the highest. It can elevate the discharge potential platform and prolongs discharge time, so the utilization ratio of Ni (OH)2 is raised.``     

Electrochemical Quartz Crystal Impedance Study of Glucose Oxidation on a Nickel Hydroxide Modified Au Electrode in Alkaline Solution

The electrochemical quartz crystal impedance (EQCI) technique has been applied to investigate glucose oxidation on bare and Ni(OH)₂‐modified Au electrodes in 0.2 mol L^?1 KOH aqueous solution. The EQCI responses suggest different contributions of H⁺‐release and OH^?‐incorporation reactions of the Ni(OH)₂‐film redox process in 0.2 mol L^?1 aqueous KOH at different potentials. Glucose adsorption on the Ni(OH)₂‐modified Au electrode was studied. A mechanism for potential cyclic redox process of glucose at Ni(OH)₂‐modified Au electrode is suggested, mainly based on a comparative EQCI analysis with direct glucose oxidation on bare gold and glucose ad‐/desorption on Ni(OH)₂ film.     

铋膜电极方波吸附溶出伏安法测定纺织品中痕量钴和镍

本文建立了在铋膜修饰电极上采用方波吸附溶出伏安法同时测定纺织品中痕量Co2+和Ni2+的方法.以NH3-NH4Cl作为缓冲液,在丁二酮肟浓度为10 μmol/L的体系中,Co2和Ni2+的还原峰电位分别为-1.13 V和-1.03 V.当缓冲溶液pH为9.2,富集电位为-0.7V,富集时间为200 s时,C02 +和Ni2+在0.5～50 μg/L范围呈现良好的线性关系,相关系数R2＞0.99,其检出限分别为0.79 μg/L和0.96 μg/L,其它金属离子的干扰较小.采用标准加入法测定纺织品中Co>和Ni2+,回收率在94.88％～104.14％之间.     

电沉积双金属微粒电极及对甲醇的电催化研究

以循环伏安法在镍铬铁基体上制备了Pt-Ru微粒电极, 用SEM表征该微粒电极的形貌呈球形, 循环伏安法和计时电流法考察了该电极的电化学性能. 结果表明Pt-Ru微粒电极对甲醇的电氧化显示出催化作用, Ru的加入提高了电极的抗中毒能力. 在相同的实验条件下, Pt-Ru微粒电极对甲醇的催化氧化性能高于纯铂电极, 且该电极制作成本十分低廉、操作简便、对环境无污染, 极大减少了贵金属铂的用量, 可用作燃料电池的电极材料.     

Ni纳米催化剂的制备及其对葡萄糖电催化氧化的研究

采用等体积浸渍和程序升温还原的方法制备了不同Ni含量的Ni/AC纳米催化剂,并对其进行了形貌和结构表征。采用三电极体系和循环伏安法在碱性溶液中进行了其对葡萄糖催化氧化的电化学测试。结果表明,Ni/AC/GCE(修饰在玻碳电极上的Ni/AC)催化剂对葡萄糖有较强的电催化氧化作用。其中,20%的Ni/AC/GCE对葡萄糖电催化氧化作用最强,且随着葡萄糖浓度增加,响应电流显著增大,二者呈线性相关。20%Ni/AC/GCE催化剂对葡萄糖催化氧化的线性响应范围为0.2~6.5 mmol/L,相关系数为0.999,响应灵敏度是13.15μA/(mmol/L),最低检测限为35μmol/L。稳定性测试结果表明,20%Ni/AC/GCE有着良好的稳定性,每隔两天测试,运行三周后其响应电流仍能维持在95%以上。     

Embedment of Well Dispersed Nickel Nanoparticles in Sulfonate and Benzimidazole Functionalized Poly (Arylene Ether Ketone) Film for the Electrocatalytic Oxidation of Glucose

Stable and well dispersed nickel nanoparticles (NiNPs) were fabricated and embedded in a novel polymer sulfonate and benzimidazole functionalized poly (arylene ether ketone) (S‐BI‐PAEK) film. After drop‐casting the mixed solution of S‐BI‐PAEK and NiSO₄ on glassy carbon electrode (GCE) surface, the uniformly distributed NiNPs were formed and stably embedded in S‐BI‐PAEK film by in‐situ electrochemical reduction method. The embedment and well dispersity of NiNPs in S‐BI‐PAEK film was probably attributed to the strong chelation of sulfonate and benzimidazole functional groups contained in S‐BI‐PAEK toward Ni²⁺ ions, as well as the transferability of Ni²⁺ ions in S‐BI‐PAEK film. The NiNPs/S‐BI‐PAEK composite film was characterized by scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). It exhibited good electrocatalytic activity toward glucose oxidation in 0.1 mol L⁻¹ NaOH solution with high stability. The NiNPs/S‐BI‐PAEK/GCE showed a fast amperometric response with a wide linear range from 1 μM to 4 mM and a low detection limit of 200 nmol L⁻¹ (S/N=3) for the determination of glucose by amperometry at a potential of 0.55 V. Finally it was successfully employed to determine glucose in human serum. Therefore, the novel fabrication method of nickel nanoparticles was promising for the future development of non‐enzymatic glucose sensor.     

新型高比能镍氢电池正极材料的表征及检测技术

讨论了影响高比能镍氢电池正极材料氢氧化镍性能的因素。确定了化学组成、密度、粒径大小及粒度分布、比表面积和组织形态等适合于表征镍氢电池正极材料氢氧化镍的参数。研究并提出这些表征参数的分析检测方法。解决了镍氢电池正极材料行业的材料标准混乱、不统一的问题，推动了行业技术进步。     

Coupling Benzylamine Oxidation with CO2 Photoconversion to Ethanol over a Black Phosphorus and Bismuth Tungstate S-Scheme Heterojunction

Photoconversion of CO₂ and H₂O into ethanol is an ideal strategy to achieve carbon neutrality. However, the production of ethanol with high activity and selectivity is challenging owing to the less efficient reduction half-reaction involving multi-step proton-coupled electron transfer (PCET), a slow C−C coupling process, and sluggish water oxidation half-reaction. Herein, a two-dimensional/two-dimensional (2D/2D) S-scheme heterojunction consisting of black phosphorus and Bi₂WO₆ (BP/BWO) was constructed for photocatalytic CO₂ reduction coupling with benzylamine (BA) oxidation. The as-prepared BP/BWO catalyst exhibits a superior photocatalytic performance toward CO₂ reduction, with a yield of 61.3 μmol g⁻¹ h⁻¹ for ethanol (selectivity of 91 %).In situ spectroscopic studies and theoretical calculations reveal that S-scheme heterojunction can effectively promote photogenerated carrier separation via the Bi−O−P bridge to accelerate the PCET process. Meanwhile, electron-rich BP acts as the active site and plays a vital role in the process of C−C coupling. In addition, the substitution of BA oxidation for H₂O oxidation can further enhance the photocatalytic performance of CO₂ reduction to C₂H₅OH. This work opens a new horizon for exploring novel heterogeneous photocatalysts in CO₂ photoconversion to C₂H₅OH based on cooperative photoredox systems.     

Co对Ni（OH）2电极中质子扩散行为的研究

本文采用恒电位阶跃，循环伏安及恒电流放电池，考察含Ｃｏ量０％－５３％的Ｎｉ（ＯＨ）２电极充电过程中质子的扩散系数：充电过程该值为１０＾－９－１０＾－１０ｃｍ＾２／ｓ，放电过程则为１０＾－１１ｃｍ＾２／ｓ．数据处理时对文献中有关公式进行了修正。