Buming CHEN
,
Zhongcheng GUO
,
Hui HUANG
,
Xianwan YANG
,
Yuandong CAO
金属学报(英文版)
doi:10.1016/S1006-7191(08)60111-8
The α-PbO2 electrodes are prepared by anodic electrodeposition on A1/conductive coating electrode from alkaline plumbite solutions in order to investigate the effect of the different current densities on the properties of α-PbO2 electrodes. The physicochemical properties of the α-PbO2 electrodes are analyzed by using SEM, EDS, XRD, Tafel plot, linear sweep voltammetry (LSV) and A.C. impedance. A compact and uniform layer of lead dioxide was obtained at the current density of 3 mA·cm-2. A further increase in current density results in smaller particles with high porosity. EDS and XRD analyses have shown that the PbO2 deposited in alkaline conditions is highly non stoichiometric, and the PbO impurities are formed on the surface layer besides the α-PbO2 . The corrosion resistance of α-PbO2 at the low current density is superior to that of the high current density. It can be attributed to a porous layer of deposited films at high current densities. When used as anodes for oxygen evolution in aqueous Zn2+ 50~g·L-1, H2SO4 150~g·L-1, the Al/conductive coating/α-PbO2 exhibits lower potential compared to Pb electrode. Al/conductive coating/α-PbO2 electrode with the best electrocatalytic activity was obtained at current density of 1mA·cm-2. The lowest roughness factor was obtained at 1 mA·cm-2.
关键词:
Alpha lead dioxide
,
null
,
null
,
null
,
null
钱岭
,
刘鹏飞
,
张乐
,
王重午
,
杨双
,
郑黎荣
,
陈爱平
,
杨化桂
催化学报
doi:10.1016/S1872-2067(17)62809-2
通过"人工光合成"过程,将太阳能转化成氢能的形式加以存储和利用,是替代传统化石能源的清洁能源的制备有效途径.其中,光电化学分解水是氢能制备的最有潜力的路径之一.n型BiVO4由于具有丰富的储量、较窄的带隙以及合适的能带位置,被称为光电化学领域的研究热点.然而,未修饰的BiVO4光阳极性能并不理想,主要原因在于载流子复合严重、导电性差以及表面催化动力学低等性质的制约.科研工作者们针对这些方面已进行了非常多的研究,例如与电子传输层的复合、产氧电催化剂的担载以及异质结的构建等.其中表面动力学和电荷分离的同时提升是更理想的改善BiVO4光阳极性能的方法.我们在上述研究基础上,采用光化学沉积法在纳米多孔BiVO4电极表面担载无定形氧化铁层,将电极在1.23 V vs.RHE电位下的光电流提升至2.52 mA/cm2,是初始光电化学性能的3倍.采用间歇光照计时电流(i-t)测试,电化学交流阻抗谱(EIS),X射线光电子能谱(XPS),原位和非原位的X射线精细结构能谱(in-situ and ex-situ XAFS)等表征手段研究了无定形氧化铁层的成分和光电化学反应过程中的价态变化,从而分析出光电化学性能提升的原因.间歇光照i-t测试和EIS测试结果表明,无定形氧化铁沉积在BiVO4使电荷累积减少,复合率降低.XPS测试结果发现无定形氧化铁层存在少量的二价铁成分.通过原位XAFS测试发现,BiVO4/FeOx电极中Fe原子的价态在光照和施加外加偏压条件下会有价态的升高,而撤去光照和偏压后Fe原子的价态状态与最初非原位的测试结果重合.这样的结果证明了无定型氧化铁层在光电化学反应过程中由于二价铁成分的存在,能够很好的通过价态改变实现空穴的吸附和传输,即吸附空穴,被空穴氧化成三价或四价,同时结合自身电催化活性,促进表面分解水反应的进行.而水的氧化反应结束时,则伴随着二价铁离子的再生成.这种反应机理为开发更高效的电催化剂,匹配光电极使用,有着重大的指导意义.
关键词:
氧化铁层
,
无定形
,
钒酸铋
,
光阳极
,
氧生成
