一步电沉积法制备Ni-Mo-Nd/NF复合电极及其析氢性能研究

目的 采用一步恒电流沉积法在泡沫镍基底上制备出镍-钼-钕三元析氢电极,提高碱性条件下的析氢性能。方法 使用电化学工作站研究工艺参数对Ni-Mo-Nd/NF析氢电极性能的影响,同时制备Ni-Mo/NF析氢电极,使用扫描电镜(SEM)、X射线衍射分析仪(XRD)、能谱仪(EDS)和X射线光电子能谱(XPS)对合金镀层表面形貌、相结构、元素含量及成键状态进行表征。通过线性扫描伏安法(LSV)、循环伏安法(CV)及电化学阻抗技术(EIS)测试电极析氢性能。结果 最佳工艺参数为:pH=4.5,电流密度30 mA/cm²,沉积时间60 min,温度30 ℃。在1.0 mol/L KOH溶液中,Ni-Mo-Nd/NF电极在10 mA/cm²下的析氢过电位仅为73 mV,Tafel斜率为147 mV/dec,表明析氢反应机理遵循典型的Volmer-Heyrovsky步骤。此外,Ni-Mo-Nd/NF电极在长时电解24 h时电流密度保持稳定,2 000次循环伏安测试后,催化剂的活性衰减微小。结论 稀土元素Nd的掺杂,能够细化电极表面的球形颗粒并提高电极表面粗糙度,从而提升电极的比表面积,为析氢反应提供更多的活性位点,利于析氢反应效率的提高。由于三元合金的协同作用,与二元合金Ni-Mo/NF相比,Ni-Mo-Nd/NF三元合金电极显示出更优异的HER催化性能。     

TiB2涂层熔盐电沉积制备与表征

炭阴极在铝电解槽中受熔盐和铝液腐蚀而影响寿命,而TiB₂涂层是铝电解槽理想的阴极材料。本文以石墨为基体,在KF-KCl-K₂TiF₆-KBF₄熔盐中以0.4-0.7A.cm_-2^{电流密度、}700-800℃温度电沉积TiB₂涂层,通过XRD衍射仪、SEM-EDS、表面粗糙度测量仪及附着力测试仪对不同电流密度和温度下制备的涂层进行表征。结果表明：在石墨基体上可以得到均匀连贯的TiB₂涂层;增大电流密度、降低电解温度可以细化涂层晶粒,提高涂层致密性;在0.6 A.cm_-²、750℃最优电沉积条件下制得的TiB₂涂层的厚度为229 μm,择优取向为<110>,表面粗糙度为14.85 μm,涂层与石墨基体的结合力为6.39 MPa。     

电流密度对ZK60镁合金表面超疏水涂层的制备及耐腐蚀性的影响

为了提高镁合金的耐腐蚀性能,基于层状双氢氧化物（LDHs）膜在ZK60镁合金表面制备了超疏水（SH）涂层。涂层制备过程中引入电场辅助,研究了工作电流密度对涂层性能的影响。结果表明,工作电流密度显著影响LDHs膜的微观结构,这对SH涂层的疏水性具有重要影响。当工作电流密度为25 mA/cm²时,SH涂层表面呈现均匀的微纳米结构,并表现出超疏水性。超疏水涂层的腐蚀电流密度（I_corr=9×10^-7 A·cm^-2）比ZK60基体的腐蚀电流密度（I_corr=3×10^-5 A·cm^-2）低了2个数量级,表现出优异的耐腐蚀性。     

1-丁基-3-甲基咪唑四氟硼酸盐离子液体电沉积制备Ir研究

本文研究了在离子液体1-丁基-3-甲基咪唑四氟硼酸盐中电沉积制备Ir的电化学行为,在金电极上获得的循环伏安特性曲线表示,Ir(III)经过一步还原反应生成Ir,并且该反应是由Ir(III)离子的扩散控制的不可逆过程。其中,扩散速率为3.83×10_?11 m₂/s,平均传质系数为0.083。本文用扫描电镜(SEM)、X-射线衍射(XRD)及X-射线光电子能谱(XPS)研究了在钼基体上获得的Ir层的表面形貌及组成,结果显示,Ir层的形貌与沉积电位、时间及电流密度有关。恒电位电沉积过程中,在还原峰电位处由于成核及生长速率达到平衡,可以获得相对致密的镀层。在恒电流电沉积中,当电流密度在0.5~1.82 mA/cm₂时可以得到平整致密的Ir镀层。     

Pdx-Co/C催化甲酸的电氧化性能研究

以活性碳(Vulcan XC-72)为载体,用化学还原法制备了不同Pd/Co摩尔比的Pdx-Co/C催化剂。用透射电镜(TEM)、X射线衍射(XRD)及X射线光电子能谱(XPS)对催化剂进行了表征,采用循环伏安法考察了催化剂对甲酸电氧化反应的催化性能。结果表明,Pdx-Co复合催化剂粒子均匀分散在碳载体表面;催化剂中掺入的少量Co元素部分进入Pd晶格,形成了Pd-Co合金;随着Pd/Co摩尔比的增加,Pd颗粒粒径先增大后减小,催化活性也表现出相同的变化趋势;当Pd:Co=8:1时,所得Pd8-Co/C对甲酸氧化的催化活性最高,峰电流密度可达到15.907 mA/cm²。     

工艺参数对低pH值2.0~2.5柠檬酸水溶液电沉积铼铱基合金薄膜特征影响

研究了在低pH值2.0~2.5的柠檬酸水溶液中恒电流电沉积富Re+Ir的Re-Ir-Ni合金薄膜特征,以及镀液温度、镀液pH、电流密度和镀液化学组成对薄膜表面形貌、化学成分和晶体结构的影响。采用环境扫描电子显微镜、X射线能谱仪和X射线衍射仪分别对合金薄膜的形貌、成分和物相进行了表征。结果表明：在电流密度为60 mA·cm^-2、pH为2.0时,获得致密光亮的Re-Ir合金薄膜。在pH=2.5时,提高镀液温度可获得质量良好的合金薄膜,而pH=2.0时,则相反。在镀液温度60~70 ℃、pH=2.0时,沉积的合金薄膜由非晶相组成;在镀液温度80 ℃时,薄膜由ReO₃相组成。在电流密度为60 mA·cm^-2、pH值从2.0增加到2.5时,合金薄膜的晶形结构由非晶态转变为晶态和非晶态的混合结构。结晶相为hcp-Ir_0.4Re_0.6和hcp-Ni。     

喷雾干燥法制备铂镍合金三维纳米骨架材料及增强甲醇氧化性能研究

本文以氯铂酸氨和氯化镍为原料,氯化铵作为造孔剂,通过雾化干燥法结合煅烧还原制备铂镍合金三维纳米骨架材料,该新型材料可增强催化甲醇氧化性能。重点研究了前驱体中加入氯化铵和不加入对铂镍合金三维纳米骨架形成的影响规律,研究不同结构的铂镍合金三维纳米骨架材料对催化氧化甲醇活性和稳定性的影响规律。研究结果表明,通过加入适量的氯化铵作为造孔剂,制备的铂镍合金为单项固溶体结构(面心立方结构),由弯曲纳米线交织组成三维纳米骨架材料,纳米线直径小于10 nm,纳米孔10 nm左右;与商用Pt黑和不加入氯化铵制备的铂镍合金纳米材料相比,PtNi合金三维纳米骨架材料具有更高的甲醇催化氧化活性(611.4 mA.mg_^-1Pt),分别是商用Pt黑的3.58倍(170.8 mA.mg_^-1Pt)和PtNi合金纳米材料(不加氯化铵)的1.36倍(448.8 mA.mg_^-1Pt);在催化甲醇氧化性能稳定性上,PtNi合金三维纳米骨架材料表现出最好的稳定性,稳定性顺序为：PtNi合金三维纳米骨架材料 > PtNi合金纳米材料(不加氯化铵)> 商用Pt黑。此外,本文对该方法进行了扩展,成功的制备了铂镍钴铜钌铱钯(PtNiCoCuRuIrPd)高熵合金三维纳米骨架材料。     

DEFORMATION BEHAVIOR OF SPRAY–DEPOSITED La–BASED BULK AMORPHOUS ALLOY IN SUPERCOOLED LIQUID REGION

研究了喷射成形大尺寸La₆₂Al_15.7(Cu, Ni)_22.3非晶合金在过冷液相区内的塑性变形行为. 结果表明, 随加热温度 的增加和应变速率的减小, 该非晶合金由非稳态变形向单一稳态变形行为转变. 当应变速率为5×10^-3 s^-1, 温度为443 K和挤压比为6.25时, 喷射成形La₆₂Al_15.7(Cu, Ni)_22.3非晶合金样品的密度由挤压前的5.723增加到挤压后的5.924 g/cm³, 达到了同成分吸铸态非晶合金密度 (6.134 g/cm³) 的96.6%. 挤压后非晶合金样品依然保持完全非晶态.     

原位粉末装管法37芯MgB2线材的制备及性能研究

传统的Cu包套原位粉末装管法(in situ PIT)制备多芯MgB₂超导线材时,易于出现断芯、断线现象。针对一问题,本实验中以强度较高的梦乃尔合金(Monel 400)作为包套材料,以旋锻、拉拔、轧制及中间热处理相结合的加工手段成功的制备出直径Φ1.0 mm、37芯结构的多芯MgB₂超导长线材。微观结构分析表明多芯线材中MgB₂芯丝及替换芯丝等亚组元的分布较为规整,阻隔层未出现明显破损现象,最终线材中MgB₂超导芯丝的平均直径约80 μm。室温拉伸性能显示热处理前MgB₂线材的屈服强度为759 MPa,热处理后的线材为248 MPa。4.2 K、4 T下,线材的临界电流密度J_c达到2.31×10^₅ A.cm^_-2,工程临界电流密度达到3.16×10^₄ A.cm^_-2。     

稀土元素添加对铁基非晶复合材料腐蚀行为影响

采用工业原料经包覆剂(CaO-Fe₂O₃-SiO₂)处理制备Fe-15Mn-5Si-14Cr-0.2C非晶复合材料棒状试样,添加稀土元素Ce、Dy及Ce+Dy,通过XRD研究稀土元素对微观组织的影响;采用电化学工作站三电极体系测试试样在1mol/L的HCl及1mol/L的NaOH中的腐蚀行为。结果表明：合金在添加稀土元素的组织依然为非晶复合材料(过冷奥氏体相CFe_15.1+ 铁素体相Fe-Cr),加入1%Ce的试样在HCl及NaOH的耐蚀性均为最佳,在HCl中自腐蚀电位为-0.16205V,自腐蚀电流密度为7.6999×10^₈A.cm^_-2,极化阻值达到9.5774×10^₈Ω.cm^₂,在NaOH自腐蚀电位和自腐蚀电流密度为-0.1839V,1.7453×10^_-8A.cm^_-2,极化阻值为7.1574×10^₈Ω.cm^₂,耐蚀性远优于AISI304,是潜力巨大的耐蚀材料。     

Surface structure and catalytic activity of electrodeposited Ni-Fe-Co-Mo alloy electrode by partially leaching Mo and Fe

1 Introduction The chlorine alkaline industry and the production of hydrogen by electrolyzing water have disadvantages of high cost and energy consumption, so it is especially important to study and develop a high catalytic activity and good stability el…     

In-situ hydrothermal synthesis of Ni–MoO2 heterostructure on porous bulk NiMo alloy for efficient hydrogen evolution reaction

The Ni–MoO₂ heterostructure was synthesized in suit on porous bulk NiMo alloy by a facile powder metallurgy and hydrothermal method. The results of field emission scanning electron microscopy (SEM), field emission transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) reveal that the as-prepared electrode possesses the heterostructure and a layer of Ni(OH)₂ nanosheets is formed on the surface of Ni–MoO₂ electrode simultaneously after hydrothermal treatment, which provides abundant interface and much active sites, as well as much active specific surface area. The results of hydrogen evolution reaction indicate that the Ni–MoO₂ heterostructure electrode exhibits excellent catalytic performance, requiring only 41 mV overpotential to reach the current density of 10 mA/cm². It also possesses a small Tafel slope of 52.7 mV/dec and long-term stability of electrolysis in alkaline medium.     

碳纳米管载钴析氢催化剂制备研究

铂基催化剂是目前应用最广泛的电解水制氢催化剂，但其储量较低、价格昂贵，从而制约了电解水技术的大规模应用和发展。为降低催化剂成本，过渡金属被广泛研究，基于此本文提出一种蒸发干燥混合溶液制备碳纳米管载钴析氢催化剂的制备方法。TEM和XRD表征结果显示，钴金属颗粒均匀分布于碳载体表面，其平均粒径大小不超过20 nm，属于典型的面心立方晶系。电化学测定结果表明，本方法制备的碳纳米管载钴催化剂具有一定的析氢性能，1 mol/L KOH溶液中，达到10和100 mA/cm²电流强度的过电位分别为180和360 mV，连续运行25 h，催化性能稳定。     

Electrodeposition of Co and CoMo alloys coatings using choline chloride based ionic liquids – evaluation of corrosion behaviour

This study deals with the electrodeposition of Co and CoMo alloys from various ionic liquids based on choline chloride (ChCl) – urea and ChCl – ethylene glycol eutectic mixtures.

The Co and Co–Mo (with 1–8?wt-% Mo content) deposits obtained were adherent, compact and uniform onto copper substrates. A decrease of the Mo content in the alloy has been shown as the applied current density increased in the range of 7–25?mA?cm^?2, at 90–100°C.

Some peaks assigned to MoO₃ or Co₃Mo phases have been identified in the XRD patterns. The average size of crystallites has been estimated to be in the range of 7–9.2?nm (nanocrystalline deposits). Atomic Force Microscopy analysis gave evidence that Co deposits were formed by multiple compact almost rounded crystallites, while Co–Mo alloy ones consisted of multiple relatively compact grains with cylindrical shape. The coatings’ corrosion performance has been also measured by continuous immersion testing in 0.5M NaCl solution, and potentiodynamic polarisation and electrochemical impedance spectra.     

V，Ru共掺杂NiS2 高尔夫微球作为碱性介质析氢反应的高效电催化剂

通过溶剂热法和滴钌法(室温)将钒和钌引入到NiS₂中,并制备了包覆在泡沫镍上的V,Ru共掺杂NiS₂微球(V, Ru)-NiS₂/NF电催化剂。通过硫化过程产生粗糙的高尔夫球状结构暴露出丰富的活性位点,此外,钒和钌的协同作用可以优化NiS₂的电子结构,提供额外的催化活性位点,进一步增强本征催化活性。泡沫镍的加入对催化材料起到支撑作用,避免聚集,同时提高导电性。结果表明,(V, Ru)-NiS₂/NF电催化剂在碱性条件下表现出优异的电催化性能和优异的析氢反应稳定性。在10 mA·cm^-2的电流密度下,(V, Ru)-NiS₂/NF提供了38 mV的过电位,小于商业Pt/C的过电位,并且具有较低的Tafel斜率(80.3 mV·dec^-1)、较高的电化学活性表面(ECSA)和在KOH溶液中24 h出色的稳定性。     

Mathematical modeling of electrodeposition of permalloy thin film I. direct current plating

A mathematical model is presented to describe the electrodeposition of Ni-Fe alloy film on a rotating disk electrode in chloride solution. The model incorporated with anomalous codeposition phenomena agrees well with the experimental data under a variety of conditions. The Fe content in permalloy shows a maximum at current densities between 2 mA/cm² and 5 mA/cm², then decreases monotonically as a function of the applied current density. Also experimental and simulated results are discussed in terms of solution pH, rotating disk speed, and iron concentration which affects the Fe content in the permalloy during electrodeposition.     

α-Ni(OH)2 electrodeposition from NiCl2 solution

α-Ni(OH)₂ was synthesized from a NiCl₂ solution by electrodeposition method. In order to conduct a systematic study on the effects of experimental parameters, a series of electrolyte initial pH values, current densities, electrodeposition temperatures, and electrodeposition time were used. Cyclic voltammetry results demonstrated a side reaction of Ni²⁺+2e→Ni. The X-ray diffraction analysis, Fourier-transform infrared spectrum, and the color of the product showed that pure α-Ni(OH)₂ could be obtained in the initial pH value range of 2–5.86, current density range of 10–25 mA/cm² electrodeposition temperature range of 25–35 °C, and electrodeposition time range of 1.0–3.0 h. When electrodeposition temperature increased to 45 °C, a mixture of α-Ni(OH)₂ and metallic Ni was obtained. A current density higher than 30 mA/cm² resulted in the sample with features of β-Ni(OH)₂. A small amount of metallic Ni existed in the as-prepared sample when current density decreased to 5 mA/cm². A slight increase of electrolyte pH was observed with increasing initial solution pH and current density. Electrodeposition mass revealed a slight decrease with initial pH decreasing and showed an almost linear increase with current density increasing. The slope of the curve for electrodeposition mass versus electrodeposition time remained stable in the first 2.0 h and then decreased.     

Production and electrochemical characterization of Ni-based composite coatings containing titanium, vanadium or molybdenum powders

Composite Ni + Ti, Ni + V and Ni + Mo coatings were prepared by codeposition of Ti, V or Mo particles in an Ni matrix on a carbon steel substrate from the nickel bath in which metallic powder was held in suspension. The influence of the metal powder amount in the bath, as well as the deposition current density on chemical composition of obtained coatings has been investigated. It was stated that the content of incorporated Ti, V and Mo increases with the increase in the particle concentration in the electrolyte, and diminishes with the increase in the deposition current density. The mechanism of metallic particles embedding was explained on the base of Ni²⁺ ions adsorption process. Deposits exhibited a presence of Ti, V or Mo microsize particles embedded into the nanocrystalline nickel matrix. Incorporation of metallic powder into electrolytic nickel matrix results in the significant increase in the real surface area of the deposits. Electrodeposited composite coatings were tested as electrode materials for hydrogen evolution reaction (HER) in an alkaline environment. Electrochemical characterization was carried out by steady-state polarization method. All composite materials showed enhanced electrochemical activity for HER compared to the nickel electrode. Based on determined values of exchange current density-j₀ and the values of hydrogen evolution overpotential at 100 mA cm^− 2-η₁₀₀ the variation in the electrochemical activity of Ni + Ti, Ni + V and Ni + Mo composites in dependence on their chemical composition and the kind of incorporated component was evaluated. Comparison of the investigated materials leads to the statement that the highest activity towards the HER exhibit Ni + Mo deposits.     

Effects of phosphate precursors on morphology and oxygen evolution reaction activity of NiFe (oxy)hydroxide on nickel foams

NiFe (oxy)hydroxides nanosheets were synthesized on nickel foams via co-precipitation and electrochemical activation. It is found that the phosphate precursors (Na₃PO₄, Na₂HPO₄ and NaH₂PO₄) have diverse effects on the morphology and thus the oxygen evolution reaction activity of the formed final catalysts. The resulting NiFe (oxy)hydroxides nanosheets prepared with Na₂HPO₄ demonstrate a low overpotential of 205 mV to achieve a current density of 50 mA/cm² with a Tafel slope down to 30 mV/dec in 1 mol/L KOH, and remain stable for 20 h during stability test.     

电沉积法制备泡沫Ni-Mo-Co合金

本文以聚氨酯泡沫海绵为基体,经导电层的制备、电镀和热解还原工艺制备出了泡沫Ni-Mo-Co三元合金.采用扫描电子显微镜(SEM)和X射线衍射技术(XRD)分别研究了化学镀镍后及电镀Ni-Mo-Co合金的表面形貌、元素组成和晶态结构,并用稳态极化曲线研究了泡沫Ni-Mo-Co合金电极在30%KOH溶液中的析氢催化性能.结...