蚀刻金属铝箔覆型制备Ni-P微阵列材料及析氢电催化性能研究

以蚀刻金属铝箔为模板,用化学镀制备了具有微米阵列结构的Ni-P合金材料,使用扫描电镜、能量散射谱及X-射线衍射等表征手段对所得材料的微观形貌与物质组成进行了分析,并通过电化学方法研究了化学镀温度、施镀时间对材料析氢催化活性的影响。结果表明,70℃制得的Ni-P微阵列材料作电极其析氢过电位最小,电流密度为15m A/cm2时比光面Ni-P镀层下降了约100m V;同时表现出最高的交换电流密度13.53×10-6A/cm2,高出光面Ni-P镀层近1个数量级;70℃施镀4h能够得到析氢过电位较低且结构完整的镀层,延长镀时没有继续提升其性能。为直观衡量材料的催化活性,在双室槽中进行了光解水析氢测试。Ni-P微阵列材料表现出良好的催化活性,析氢速率较光面电极上升约200%。     

电沉积多孔复合Ni-P/LaNi5电极及其析氢电催化性能

采用复合电沉积制备了Ni-P/(LaNi₅+Al) 复合镀层, 然后将镀层浸泡在浓碱液中除铝, 成功得到多孔复合Ni-P/LaNi₅电极. 通过扫描电镜(SEM)、能谱分析(EDS)和X射线衍射(XRD)仪等技术表征了电极的表面形貌、组成和相结构. 运用电化学线性伏安扫描(LSV)、恒电位电解、电化学阻抗谱(EIS)等手段研究了电极在20%(w) NaOH溶液中的析氢反应(HER)电催化性和稳定性. 结果表明, 与多孔Ni-P 电极相比, 多孔复合Ni-P/LaNi₅电极具有低的析氢过电位、高的比表面积和高的稳定性能; 多孔Ni-P/LaNi₅电极的析氢反应的表观活化自由能为35.44 kJ·mol^-1, 低于多孔Ni-P 的值(50.91 kJ·mol^-1).     

纳米晶Ni-Mo合金复合镀层中钼含量对析氢反应的影响

本文利用复合电镀的方法, 将用高能机械球磨制备的纳米晶Ni-Mo合金粉制成对析氢反应有高催化性的电极。用X射线衍射仪、X射线光电子能谱仪测试了这些纳米晶的大小及复合镀层的组成, 用稳态极化曲线及交流阻抗技术测试了这些电极析氢的电化学特性。实验结果表明: 在本文研究的范围内镀层中钼含量的增加可以提高电极析氢的催化活性, 电化学脱附是这些电极上析氢反应速度的决定步骤。     

钛基PbO2+nano-WO3电极材料的复合共沉积及析氧活性

利用复合共沉积法,在涂有中间层SnO2-Sb2O5的Ti基体上制备了PbO2+nano-WO3复合电极材料.采用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和双电层电容法等对复合电极表面的组成、结构、形貌及有效电化学面积进行测试.结果表明,随着纳米WO3掺杂量逐渐增大,复合电极的表面粗糙度和孔隙率逐渐变大,电化学有效面积也随之增大;利用线性扫描及Tafel曲线等电化学测试方法研究了nano-WO3的掺杂对复合电极析氧活性的影响,结果表明,掺杂nano-WO3的复合电极较纯PbO2电极的析氧活性大幅提高,其起始析氧电位发生负移,析氧过电位下降,最大可降低近300 m V.     

Ni-W-TiO2复合电极在碱性介质中的析氢电催化性能

具有较高的析氢电催化活性的镍基多元合金材料已广为报道。近年来通过复合电沉积技术在电极中掺入RuO2、ZrO2、WC等非溶性固体微粒制备的复合功能电极材料用于析氢方面的研究已有报道,这些复合电极对析氢反应都有明显的催化作用。但是用电沉积的方法在电极中掺入TiO2制备的复合功能材料的研究还未见报道,本文研究了Ni-W-TiO2复合电极的制备、形貌结构以及在碱性介质中的析氢电催化活性和电化学稳定性。     

球磨形成的Ni-Mo纳米晶复合镀层上的析氢反应

采用复合电镀的方法将不同球磨时间制备的高催化活性的纳米晶，Ｎｉ－Ｍｏ合金粉直接镀于电极表面，并用稳态极化曲线及交流阻抗技术测试了这些电极析氢的电化学活性，同时用Ｘ射线衍射，透射电镜及扫描电镜监测了Ｎｉ－Ｍｏ合金粉的物相结构，晶粒尺寸及复合电极表面的形貌，并初步探讨了这些复合电极的析氢机理，实验结果表明，球磨不仅可使镍钼粉合金化成为纳米晶，同时随着球磨时间的增加，纳米晶晶粒继续细化，电极的析氢催化活     

在纳米晶Co－Mo／Ni复合电极上的析氢反应

采用复合电镀的方法将不同球磨时间制备的高催化活性的纳米晶Ｃｏ－Ｍｏ合金粉直接镀在电极表面,用稳态极化曲线及交流阻抗技术测试了这些电极析氢的电化学活性,并用Ｘ射线衍射、透射电镜及Ｘ射线光电子能谱、扫描电镜监测了Ｃｏ－ＭＯ合金粉的物相结构、晶粒尺寸和复合镀层的成份、形貌,实验结果表明,Ｃｏ－Ｍｏ纳米晶合金粉有较高的析氢催化活性。球磨使钴钼粉合金化成为纳米晶,一方面增加了复合镀层的真实表面积,另一方面由于纳米晶合金具有高比例的表面活性原子,致使析氢活化能降低,加快了析氢反应,研究表明在不太高温度下,电化学脱附的活化能和整个析氢反应的活化能一致。说明电化学脱附为速度控制步骤。     

聚对氨基苯磺酸修饰石墨毡电极在全钒液流电池中的应用

通过电聚合和高温碳化的方法在石墨毡电极碳纤维表面修饰对氨基苯苯磺酸。用扫描电镜和电化学工作站分别表征了材料的表面形貌和电化学性质。结果表明:在石墨毡纤维表面均匀的分布着聚对氨基苯磺酸反应位点;电极不仅对V~(3+)/V~(2+)与VO~(2+)/VO_2~+电对具有很好的电催化性能,而且有效抑制了负极析氢过程,该电极在电流密度为180 m A/cm2情况下,能量效率为70%,表现出优异的综合电化学性能。     

RuO2修饰纳米多孔Ni-Mo复合电极及其电催化析氢性能

采用脱合金化结合胶体聚沉的方法制备了纳米多孔Ni/RuO_2、Ni-Mo/RuO_2复合电极材料。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、透射电镜(TEM)对电极材料的物相、元素组态、形貌结构、孔径大小和结晶度进行表征,并通过线性扫描伏安、交流阻抗以及循环伏安等方法测试多孔电极的电催化析氢性能。分析结果显示:RuO_2由于聚沉作用包覆在Ni基合金的骨架表面。Mo的加入使Ni-Mo合金非晶化的同时,促使其骨架细化,形成双连续的纳米多孔结构。Mo与RuO_2的加入以及Mo含量的增加均提高了电催化析氢性能。纳米多孔Ni_(2.5)Mo_(2.5)/RuO_2复合电极在50 mA·cm~(-2)的电流密度下析氢过电位为182 mV。     

Ni-Co-LaNi5复合电极材料在碱性介质中的电催化析氢性能

电催化析氢反应是电能向化学能转化的一个有效途径,是电化学科学中一个非常值得深入研究的课题。阴极析氢超电势的降低,是提高析氢活性,降低电解能耗的关键。为了提高电极的电催化活性,一是可通过提高电极表面的真实表面积,来降低电解过程中电极表面的真实电流密度,达到降低析氢超电势的目的;另一发展方向是提高电极材料本身的电化学活性,即寻找高催化活性的新型析氢材料犤1犦。由于过渡金属具有特殊的d电于结构,是目前公认的电化学活性最好的电极材料,而在过渡金属中,Ni及Ni合金将是研究的主要方向,其中多元合金复合材料将成为该技术发展…     

Ni-P-TiO2化学复合镀层电极的乙醇电催化氧化

于Ni-P镀液添加TiO2颗粒,用化学镀法在黄铜基底上制备不同TiO2含量的Ni-P-TiO2复合镀层电极.采用循环伏安法、线性扫描法、计时电流和交流阻抗法测定Ni-P-TiO2/Cu电极的电化学性能.结果表明:常温下Ni-P-TiO2/Cu电极在碱性溶液中对乙醇氧化有很高的电催化活性;Ni-P-TiO2电极上乙醇的电催化氧化活性随镀层TiO2量的不同而异;镀液中TiO2含量为5 g.L-1时,所得电极的电催化乙醇氧化的活性最佳.     

Graphite felt modified with electroless Co-Ni-P alloy as an electrode material for electrochemical oxidation and reduction of polysulfide species

Electroless deposition of a Co?Ni?P alloy on the surface of graphite felt filaments was performed in a low-temperature pyrophosphate solution under flow-through conditions. The loading, composition, morphology, and structure of electroless the Co?Ni?P alloy deposit on the filaments of the modified graphite felt were investigated by gravimetric analysis, energy-dispersive X-ray spectroscopy, scanning electron microscopy and X-ray diffraction, respectively. Electrochemical characterization of a graphite felt electrode modified with electroless Co?Ni?P alloy was performed by cyclic voltammetry, chrono-techniques, and the electrochemical impedance spectroscopy test in an aqueous solution of polysulfide composed of the mixture of 1 M Na₂S, 1 M NaOH and 1 M S. It was found that the electroless Co?Ni?P alloy deposit on graphite felt has good cycling stability and high electrocatalytic activity toward reversible electrochemical redox reactions of polysulfide species. In comparison with the bare graphite felt electrode, the electrode modified with the electroless Co?Ni?P alloy showed five to seven times lower values of anodic and cathodic overpotentials in the aqueous solution of polysulfide. It is very likely that the good electrochemical performance of the modified graphite felt electrode is related to the high surface area of the electroless Co?Ni?P alloy deposit.     

Ni-P化学镀反应速率及机理研究

通过镀层分析和析氢量测量得到Ni-P镀层的沉积速度和H2PO2的分解速度·以混合电位理论为基础，对Ni－P电极在不同组成饮液中的极化曲线进行分解得到以化学镀电流形式所表示的反应速率·将两种方法所得结果进行对照，确定H2PO2氧化时电子迁移数为1，并用原子红-电化学联合理论解释溶液PH对反应速率及化学镀效率的景响．     

High-electromagnetic-shielding cotton fabric prepared using multiwall carbon nanotubes/nickel–phosphorus electroless plating

High-electromagnetic-shielding cotton fabric (CF) was prepared using carboxyl-functionalized multiwall carbon nanotubes (MWCNTs-COOH)/nickel–phosphorus (Ni-P) electroless plating. Firstly, MWCNTs-COOH was loaded on CF used to chelate the metal catalyst followed by electroless plating to impart outstanding electrical conductivity and electromagnetic shielding properties. The intermediate MWCNTs-COOH layer not only improves the bonding strength via the chelating effect, but also can be used as a conductive material. This synergistic action of MWCNTs-COOH and Ni-P layer can work together to improve the electromagnetic interference shielding performance. The features of Ni-P/MWCNTs-COOH/CF were characterized using scanning electron microscopy, energy-dispersive spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The resulting Ni-P/MWCNTs-COOH/CF fabrics show high surface resistance of 1.66 Ω sq⁻¹ and robust electromagnetic shielding effectiveness of 40.2 dB. Furthermore, benefiting from the strong interface interaction, the as-prepared composite fabrics retain stable performances after undergoing a series of physical and chemical tests, confirming promising practical applications even under harsh conditions.     

Effect of 3-S isothiuronium propyl sulfonate on electroless nickel deposition

The effects of organic additive, 3-S isothiuronium propyl sulfonate (UPS) on bath stability, deposition rate, reaction activation energy, and Ni-P coating composition in acidic electroless nickel (EN) plating were investigated. The study was performed by measuring the polarization curves and X-ray fluorescence spectrometer (XRF) in combination with X-ray photoelectron spectroscopy (XPS) analysis. The results show that UPS improves bath stability and increases the reaction activation energy. At lower concentration, UPS is an effective accelerator for EN deposition; whereas, at higher concentration, it decreases deposition rate. It also reveals that UPS inhibits the anodic oxidation of hypophosphite and accelerates the cathodic reduction. In addition, UPS decreases the phosphorus content in Ni-P deposit and can be adsorbed on the deposit surface and compound with Ni²⁺. On the basis of these results, the effect mechanism of UPS on electroless nickel deposition was deduced.     

电沉积Ni/LaNiO3复合电极及其在碱性介质中的析氧性能

采用溶胶-凝胶法制备了钙钛矿型复合氧化物LaNiO3,然后将其加入瓦特镀镍液中进行复合电沉积,研究了镀液pH值和阴极电流密度对Ni/LaNiO3复合镀层组成的影响。运用扫描电镜(SEM)、能谱分析(EDS)和X射线衍射(XRD)等对复合镀层进行表征,结果表明:最佳电沉积工艺条件是镀液pH=5.8和阴极电流密度jk=90 mA.cm-2,所得的Ni/LaNiO3复合镀层中LaNiO3的质量含量约为60%。用循环伏安、稳态极化、恒电位阶跃、电化学阻抗谱等电化学技术评价了Ni/LaNiO3复合电极的析氧性能。结果表明:在5 mol.L-1的KOH溶液中,Ni/LaNiO3复合电极的起始析氧电位较镍电极负,表观活化自由能比镍电极降低约2/3,比表面积约为镍电极的55倍,析氧电催化性能得到大幅度提高。     

负载型纳米Ni催化剂用于对氯硝基苯选择加氢

以TiO2为载体,N iB为诱导剂,粉末化学镀法制备了负载型纳米N i催化剂.通过TEM、HRTEM、XRD和ICP技术对催化剂物性进行了表征.结果表明,碱性镀液可使载体表面均匀负载微晶结构纳米N i团簇,尺度为35nm左右.该负载型纳米N i在对氯硝基苯选择加氢反应中表现出很高催化加氢活性,并能有效抑制脱氯,达到了工业骨架镍水平.由酸性镀液得到的负载型非晶态纳米N i-P合金具有较弱的催化对氯硝基苯加氢活性.反应温度对反应时间和脱氯率有明显影响.     

NH4F对化学镀镍液的作用机理及镀层性能的影响

氟元素是周期表中最活泼的非金属元素,有着最强的电负性,氟化物有着特殊的化学性能。关于氟化物在化学镀镍磷工艺中的应用已有报道,在镁基体上化学镀的前处理过程中,常用氢氟酸或氟化氢铵来进行活化处理;硅片表面上的化学镀也通常用HF与HNO3或HCl的混酸来活化,使硅片表面产生Si-H键。另外,如果在化学镀液中添加少量的氟化钠,则起到加速的作用[1]。对于氟化物在化学镀镍磷工艺中的报道仅限于此,未见有关氟化物在化学镀中其它作用的研究。鉴于此,本工作以氟化铵为研究对象,对其在弱碱性的条件下对化学镀液的缓冲能力、沉积速度以及所得镀层性能的影响进行了研究。     

Diamond-structured hollow-tube lattice Ni materials via 3D printing

Light-weight and high-strength materials have attracted considerable attention owing to their outstanding properties, such as weight-reducing, acoustic absorption, thermal insulation, shock and vibration damping. Diamond possesses specific stiffness and strength arising from its special crystal structure. In this work, inspired by the diamond crystal structure, hollow-tube nickel materials with the diamond structure were fabricated using a diamond structured polymer template based on the Stereo Lithography Appearance technology. The diamond structured template was coated with Ni-P by electroless plating. Finally, the template was removed by high temperature calcinations. The density of the hollow tube nickel materials is about 20 mg/cm3. The morphology and composition of the resultant materials were characterized by scanning electron microscope, energy-dispersive spectrometry, and X-ray diffraction. The results showed that the surface of the Ni film was uniform with the thickness of 4 μm.The mechanical property was also measured by stress and strain tester. The maximum compression stress can be reached to40.6 KPa.