电沉积非晶态Co-W合金镀层在碱性溶液中的电催化析氢研究

利用恒电流直流电沉积方法在Cu基底表面制备了Co-W合金镀层,当镀液中WO_4~(2-)浓度≥0.075 mol/L时镀层为非晶态结构。电化学研究表明,非晶态Co-W合金镀层在1 mol/L NaOH溶液中表现出良好的电催化析氢活性,过程受Volmer-Heyrovsky路径控制。W含量约为40.1%(质量分数)的Co-W合金镀层析氢活性最强,其表观交换电流密度j_0为3.17×10~(-5)A/cm~2;当电位负于-1.464 V(相对于饱和甘汞电极电位)后该Co-W合金镀层的阴极电流密度超越了商用Pt片。结合电化学阻抗分析获知,由于镀层本征催化活性和比表面积(或电化学活性面积)均得到提升,使得非晶态Co-W合金镀层析氢活性获得提高。     

化学镀Ni-Co-W-P及其析氢性能的研究

用化学镀方法制备出Ni-Co-W-P合金电极,测量了其在1 mol/L NaOH溶液中的阴极极化曲线并研究了其析氢电催化活性.试验表明,在相同的电流密度下,Ni-Co-P,Ni-W-P和Ni-Co-W-P合金电极的析氢过电位较Fe电极降低,其中Ni-Co-W-P的析氢过电位降低约230 mV,XRD试验显示其镀层为非晶态.并进一步测试了其在7 mol/L KOH中的连续电解曲线.结果表明:Ni-Co-W-P合金电极比Ni-Co-P,Ni-W-P合金电极具有更好的析氢电催化活性和电化学稳定性,有利于降低槽压,减少能耗.     

喷射电沉积镍的阴极极化行为

通过阴极极化曲线的测定研究了硫酸盐电解液喷射速度u(流速)对阴极过电位ηC和沉积层晶粒尺寸的影响.结果表明,电解液流速增大,有利于氢还原析出,导致过电位显著增大,晶粒尺寸减小.当电流密度为140 A/dm2时,喷射速度由0.83 m/s增大到5.00 m/s,阴极过电位从1.48 V增至8.52 V;晶粒尺寸从22.6 nm减小到18.9 nm.随电流密度增大,阴极上析氢步骤逐渐取代水合镍离子电化学还原步骤并成为整个过程的控制步骤.     

酸刻蚀泡沫镍增强磷化镍的析氢催化性能

氢能作为一种资源丰富、高能、无污染的"绿色能源",被认为是后石油时代解决能源和环境危机的理想能源之一。选择三维结构的泡沫镍(NF)为基底,采用0.3%(质量分数)氢氟酸(HF)对NF表面进行化学刻蚀,"开凿"形成比表面积高、电解液和析出气体易扩散的开放结构,联用固相还原法进行原位磷化,获得一体化Ni_2P/E-NF催化电极。实验结果表明,形成的一体化Ni_2P-NF催化电极避免了使用粘结剂,电极表面结构粗糙度是未刻蚀NF的2.8倍,暴露的活性位点多,在碱性条件下显示出较高的析氢反应(HER)活性,其起始析氢过电位约27mV,在电流密度达到10mA/cm~2时,析氢过电位也只有约63mV,经过4 000圈循环伏安扫描依然保持良好的稳定性。     

泡沫镍负载NiFeMoCu析氢阴极电极材料的电化学制备研究

以泡沫镍(NF)为基板,分别通过恒电位法(i-t)和计时电位法(CP)沉积镍铁钼铜四元合金,经去合金化处理,获得了具有高催化活性的析氢阴极电极材料NiFeMoCu/NF。电沉积过程设计了6种电解液配方进行优选,去合金化处理时采用恒电位法(i-t)分别进行了金属铜的原位溶出和独立溶出。结果表明:参照配方4的物料配比组织电解液,以计时电位法沉积四元合金,经铜的独立溶出后制得了由纳米颗粒堆积而成团簇状结构的析氢电极材料。在1mol/L KOH溶液中,催化电流密度为10mA/cm~2时,NiFeMoCu/NF电极的析氢过电位仅为65mV,其高催化活性主要归因于镍铁钼铜四元合金的金属间协同作用。     

AC/ Ni-Co 复合电极材料的制备及其催化析氢性能

采用复合电沉积法制备了AC(活性炭) / Ni-Co 复合电极。XRD 和SEM 测试结果表明, AC 微粒的复合未改变Ni-Co 合金电极的物相结构, 但使镀层的表面粗糙度和真实表面积增大。通过稳态阴极极化曲线和电化学交流阻抗技术考察了不同电极在1 mol·L-1 NaOH 溶液中的催化析氢性能, 结果表明, 镀液中AC 含量为3 g·L-1时所制备的AC/ Ni-Co 复合电极较Ni 电极和Ni-Co 合金电极具有更高的催化析氢活性, 电流密度为30 mA·cm-2时, 析氢反应极化电位分别比Ni 电极和Ni-Co 合金电极正移230 mV 和140 mV , 表观交换电流密度分别是Ni 电极和Ni-Co 合金电极的42 倍和9 倍, 复合电极催化析氢性能的提高主要归因于电极真实表面积的增大。      

脱合金化制备纳米多孔Ni-Fe合金及其电催化性能

采用真空熔炼与固溶相结合的方法获得原子分数为Ni_30-xFe_xMn₇₀(x=0,10,20)的前驱体合金,通过脱合金化方法制备纳米多孔Ni及Ni-Fe合金,采用X射线衍射(XRD)、扫描电子显微镜(SEM)分析合金相组成和微观结构,运用线性扫描伏安法、交流阻抗、方波电位法及计时电位法研究电极的析氢电催化性能。结果表明:加入Fe获得了片状结构的纳米多孔Ni-Fe合金,提高了纳米多孔Ni的表面积,且Fe与Ni产生协同效应,能够有效提高合金的析氢电催化活性。当Fe含量为10%(原子分数)时,脱合金化得到的纳米多孔Ni-Fe合金表面积最大,析氢电催化性能最好,在0.1A/cm^2电流密度下,析氢过电位仅56mV,经10h连续电解,表现出良好的电催化活性和电化学稳定性。     

Pb-0.3%Ag/Pb-Co_3O_4复合惰性阳极材料的电化学性能EI北大核心CSCD

在Pb-0.3%Ag合金基体表面制备了Pb-0.3%Ag/Pb-Co_3O_4复合惰性阳极材料,研究了不同正向脉冲平均电流密度(2-5A·dm^(-2))和镀液中Co_3O_4颗粒浓度(10-40 g/L)下制备的复合惰性阳极材料电化学性能,在50 g·L^(-1)Zn^(2+),150 g·L^(-1)H_2SO_4,35℃溶液中测试了阳极极化曲线、循环伏安曲线和塔菲尔曲线,获得了析氧动力学参数、伏安电荷、腐蚀电位和腐蚀电流。结果表明:在3 A/dm^2正向脉冲平均电流密度和30 g/LCo3O4颗粒浓度下制备的Pb-0.3%Ag/Pb-Co_3O_4复合惰性阳极材料具有较高的电催化活性,较低的析氧过电位,较好的电极反应可逆性和耐腐蚀性。在500 A/m^2测试电流密度下的析氧过电位为0.891 V,比Pb-1%Ag合金降低280 mV;伏安电荷q~*为0.725 C·cm^(-2),比Pb-1%Ag合金提高26.5%;腐蚀电流也明显低于Pb-1%Ag合金。复合惰性阳极材料活性表面积大,活性物质数量多提高了在[ZnSO_4+H_2SO_4]溶液中的析氧电催化活性。沉积层晶粒细小而均匀,组织结构致密,真实表面缺陷少提高了耐腐蚀性。     

电沉积制备Ni-S涂层电极的研究

以泡沫镍为基体电沉积制备了Ni-S涂层电极.通过对电流密度、电沉积温度、电沉积时间和镀液pH值等条件对涂层析氢性能影响的研究,确定了适宜的电沉积工艺条件;电极涂层的XRD、SEM测试结果表明涂层为非晶态结构、表面颗粒大小均匀且具较大表面积;电解过程中出现了Ni3S2由非晶态向晶态的转变,由于Ni3S2具有较强的吸附氢能力,是析氢反应的催化活性中心,电解过程中Ni3S2的出现降低了电极的析氢电位.模拟电解水实验结果表明泡沫镍基Ni-S涂层电极较Raney-Ni电极具有更好的析氢活性.     

NiS2@MoS2/CC纳米复合材料的制备及其电催化析氢性能的研究

电解水产氢是近来研究的热点,电极催化材料是影响析氢反应的重要因素。通过两步水热法,成功在碳布上合成了NiS_2@MoS_2三维异质结构复合催化剂(NiS_2@MoS_2/CC)。在碳布上垂直排列的NiS_2纳米片为MoS_2提供了良好的支撑,在暴露更多边缘活性位点的同时,也为析氢反应提供了快速的物质传输通道。合理的界面设计促使NiS_2和MoS_2发挥协同作用,改善催化剂表面电子状态,从而体现出更好的析氢催化活性。电化学测试表明,NiS_2@MoS_2/CC具有较大的电化学活性面积,在碱性条件下驱动10mA/cm~2析氢反应电流密度的过电位为106 mV,Tafel斜率为61.1 mV/dec,远优于单一的MoS_2/CC和NiS_2/CC催化材料。     

3D hierarchical NiS_2/MoS_2 nanostructures on CFP with enhanced electrocatalytic activity for hydrogen evolution reaction

The electrocatalytic activity for hydrogen evolution reaction(HER) is strongly correlated with active edge sites and resulting efficient charge transport capability. Here, we presented a facile two-step method to synthesize 3 D hierarchical NiS_2/MoS_2 composite nanostructures on a carbon fiber paper(CFP) skeleton.The nanostructures distributed on CFP uniformly and composed of 2 D nanosheets, which would provide plenty of active edge sites and increase the HER activity. Electrochemical measurement suggests that the prepared NiS_2/MoS_2 exhibit great HER activity including a low overpotential of 102 m V, a small Tafel slope of 67 m V/dec, and a high double-layer capacity of 53.7 m F/cm~2 in 1 M KOH aqueous solution. In addition,the HER activity is almost unchanged after galvanostatic technique with applied current densities of10 m A/cm~2 for 20 h.     

Self-supporting hierarchically micro/nano-porous Ni_3P-Co_2P-based film with high hydrophilicity for efficient hydrogen production

Designing efficient and stable non-precious metal HER(hydrogen evolution reaction)electrocatalysts with high large current density adaptability is significant for industrial application of hydrogen production by water electrolysis.Herein,a facile strategy was developed to construct a multi-phase Ni3 P-Co₂P-(Ni-Co)film with self-supporting hierarchically micro/nano-porous structure by using bubble template method electrodeposition of self-supporting micro-porous Ni Co P film,oxygen-free annealing for phase separation producing Ni₃P-Ni-Co₂P-Co structure,and acid etching for constructing surface nano-porous structure.The effective active sites for HER was significantly increased due to the hierarchically micro/nano-porous structure,which not only enlarged the surface roughness,but enhanced the bubble detachment by improving the hydrophilicity.Meanwhile,the HER electrolysis durability was improved benefiting from the Ni₃P-Co₂P phases with high corrosion resistance(especially in acid solution)and the self-supporting film structure without binder.Consequently,the Ni Co P-OA-AE film exhibited high HER catalytic performance,which delivered a current density of 10 m A cm^-2at a low overpotential of 42.9 and 39.7 m V in 1 M KOH and 0.5 M H₂SO₄,respectively.It also possessed high long-term electrolysis durability,and the cell voltage of water electrolysis using self-supporting porous Ni Co P-OA-AE||Ir O₂-Ta₂O₅ electrolyzer at 500 m A cm^-2for 250 h in 0.5 M H₂SO_(4 )is only 2.9 V.     

一种新型活性阴极材料的制备和性能

用电沉积法制备了以Ni为主的多元合金活性阴极涂层，其表面形貌为球状堆积，有利于气体溢出，减少气泡帘电阻，降低气体析出电位．该合金涂层由于本身对气体析出具有催化活性，析氢电位低、与基体结合力强、抗停断电能力强并且使用寿命长．     

A novel nanocomposite Mo–4%La2O3 cathode

A novel nanocomposite Mo–4%La₂O₃ cathode has been prepared by sol–gel method and hydrogen reduction process and then hot-pressing sintering technique. The lanthana particles in the nanocomposite cathode were less than 100 nm, and they were about 300–400 nm in the coarse-grained cathode. The particle size of lanthana has a strong effect on the field emission characteristics of cathode. The nanocomposite cathode has superior field electron emission ability than that of the coarse-grained cathode. The sites of field electron emission of the nanocomposite cathode nearly extend over the whole surface of cathode, whereas the emission sites of the coarse-grained cathode concentrate on a small area of the cathode surface. The reasons for the different distribution of emission sites were discussed.     

Corrosion fatigue behaviors of steel wires used in coalmine

The corrosion fatigue (CF) behaviors of the mining steel wire in different solutions at different applied polarization potentials were investigated in this paper. The surfaces and fracture morphologies of the steel wire at different applied potentials were observed by scanning electron microscope (SEM). The results showed that the CF life of steel wire in acid solution is the shortest. Moreover, the strong anodic polarization potential greatly reduced the CF life of steel wire, while the strong cathode potential did not reduce the CF life. For the smooth steel wire, the hydrogen impacted mainly on the plastic deformation of the wire surface. There was obvious dimple in the fatigue source zone of the wire when coupled with anode potential, and the area of the dimple increased with the increase of the applied anode potential. Conversely, the fatigue source zone of the fracture was relatively smooth at cathode polarization potential, which indicated that the crack propagation followed the mechanism of hydrogen induced cracking.     

丰富氧缺陷MnO_(x)掺杂的碳纳米纤维基锌离子电池阴极材料的制备及性能EI北大核心CSCD

可充电水系锌离子电池(ZIBs)由于性能优良、价格低廉、环境友好等优点而被广泛研究,而针对高容量、长循环寿命的ZIBs阴极结构设计成为该领域研究的热点。采用同轴静电纺丝法,以PAN溶液为皮层,含有Mn(NO_(3))_(2)·xH_(2)O的PAN溶液为芯层制备纳米纤维膜,并对其炭化后得到了一种表面具有类皮脂腺凸起结构的碳纳米纤维(MCNFs),在其表面电化学沉积MnO_(2),制得了与电解液具有优良亲和性的MnO_(2)@MCNFs阴极材料。研究表明:设计得到的类皮脂腺结构不仅增大了阴极比表面积,而且在MCNFs基底与电化学沉积的α-MnO_(2)活性物质之间形成铆接效应,加固了界面结合,减少活性物质脱落,降低界面电阻,缩短了电子传导和离子扩散路径。对其电化学性能进行测试,芯层Mn(NO_(3))_(2)·xH_(2)O含量为3%的阴极在100 mA/g的电流密度下,首周次比容量达581.16 mAh/g;在1 A/g电流密度下循环1000周次后比容量仍大于120 mAh/g,库仑效率保持在99%左右。     

退火处理对AZ31镁合金表面Ni-Mo-P镀层组织与耐腐蚀性能的影响

为了进一步提高镁合金表面Ni-Mo-P镀层的耐蚀性,采用0M、XRD和浸泡试验等方法,研究了退火处理对AZ31镁合金表面Ni-Mo-P镀层组织与腐蚀性能的影响。结果表明:AZ31镁合金阳极氧化-化学镀Ni-Mo-P镀层表面为“胞状”组织,随着退火温度的升高或退火时间的延长,AZ31镁合金阳极氧化-化学镀Ni-Mo-P镀层的胞状组织逐渐细化,但镀层厚度降低,同时,非晶态Ni-Mo-P镀层组织逐渐向晶态转变,350℃退火1.0h具有较高的非晶化程度,退火处理后的Ni-Mo-P镀层由Mg、MgO、Mg2SiO4、Ni和Ni3P组成;退火使AZ31镁合金阳极氧化-化学镀Ni-Mo-P镀层耐蚀性降低,350℃退火1.0 h镀层具有相对较好的耐蚀性,这与镀层的厚度和非晶化程度有关。     

UIO‐66‐NH2‐Derived Mesoporous Carbon Catalyst Co‐Doped with Fe/N/S as Highly Efficient Cathode Catalyst for PEMFCs

Efficient, low‐cost catalysts are desirable for the sluggish oxygen reduction reaction (ORR). Herein, UIO‐66‐NH₂‐derived multi‐element (Fe, S, N) co‐doped porous carbon catalyst is reported, Fe/N/S‐PC, with an octahedral morphology, a well‐defined mesoporous structure, and highly dispersed doping elements, synthesized by a double‐solvent diffusion‐pyrolysis method (DSDPM). The morphology of the UIO‐66‐NH₂ precursor is perfectly inherited by the derived carbon material, resulting in a high surface area, a well‐defined mesoporous structure, and atomic‐level dispersion of the doping elements. Fe/N/S‐PC demonstrates outstanding catalytic activity and durability for the ORR in both alkaline and acidic solutions. In 0.1 m KOH, its half‐potential reaches 0.87 V (vs reversible hydrogen electrode (RHE)), 30 mV more positive than that of a 20 wt% Pt/C catalyst. In 0.1 m HClO₄, it reaches 0.785 V (vs RHE), only 65 mV less than that of Pt/C. The catalyst also exhibits excellent performance in acidic hydrogen/oxygen proton exchange membrane fuel cells. A membrane electrode assembly (MEA) with the catalyst as the cathode reaches 700 mA·cm^‐2 at 0.6 V and a maximum power density of 553 mW·cm^‐2, ranking it among the best MEAs with a nonprecious metal catalyst as the cathode.     

Cobalt Iron Hydroxide as a Precious Metal‐Free Bifunctional Electrocatalyst for Efficient Overall Water Splitting

Highly efficient and stable electrocatalysts from inexpensive and earth‐abundant elements are emerging materials in the overall water splitting process. Herein, cobalt iron hydroxide nanosheets are directly deposited on nickel foam by a simple and rapid electrodeposition method. The cobalt iron hydroxide (CoFe/NF) nanosheets not only allow good exposure of the highly active surface area but also facilitate the mass and charge transport capability. As an anode, the CoFe/NF electrocatalyst displays excellent oxygen evolution reaction catalytic activity with an overpotential of 220 mV at a current density of 10 mA cm^?2. As a cathode, it exhibits good performance in the hydrogen evolution reaction with an overpotential of 110 mV, reaching a current density of 10 mA cm^?2. When CoFe/NF electrodes are used as the anode and the cathode for water splitting, a low cell voltage of 1.64 V at 10 mA cm^?2 and excellent stability for 50 h are observed. The present work demonstrates a possible pathway to develop a highly active and durable substitute for noble metal electrocatalysts for overall water splitting.