Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, College of Physics, Jilin Normal University, Siping 136000, People's Republic of China.
Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, College of Electronic Science and Information Technology, Jilin Normal University, Siping 136000, People's Republic of China.
Nanotechnology. 2023 Feb 15;34(18). doi: 10.1088/1361-6528/acb716.
Lanthanide (Ln) rare Earth (RE) elements are often used to incorporate and regulate the local coordination environment and electronic configuration of transition metal based electrocatalysts for acquiring improved electrocatalytic performance. But for a given pristine electrode, is a Ln element concentrated more on promoting the apparent activity of original electrode or on enhancing its specific activity? To address this issue, Ln (La, Ce and Nd) decorated ZIF-67 derivative electrodes (Ln/Co/NC) were fabricated following with the detailed experimental testing of apparent activity and specific activity of assembled electrodes. X-ray photoelectron spectroscopy data confirmed that Ce, Nd and La have played their own role in regulating the coordination electronic structure of the surface atoms of the derived Co/NC by forming different types of chemical bonds. Electrochemical (EC) results confirmed that Ce is concentrated more on the apparent activity of derived Co/NC electrode with the smallest overpotential at 50 mA cm(), while Nd contributes more to its reaction kinetic property with the smallest value of Tafel slope in alkaline hydrogen evolution reaction process. But for oxygen evolution reaction, all of La, Ce and Nd deteriorate the apparent activity of the pristine Co/NC electrode. Comparatively, La shows a greater ability to modulate the specific activity of Co/NC with a larger electrochemical active surface area normalized current density, while Nd exhibits the best ability to re-establish the properties of reaction centers. This work illustrates the difference influence of La, Ce and Nd on the apparent activity and specific activity of the ZIF-67 derivative Co/NC electrode. It will do some favors in engineering RE elements modified composite electrodes for EC applications.
镧系（Ln）稀土（RE）元素通常用于掺入和调节过渡金属基电催化剂的局部配位环境和电子构型，以获得改进的电催化性能。但是，对于给定的原始电极，Ln 元素是更集中于促进原始电极的表观活性还是增强其比活性？为了解决这个问题，通过详细的组装电极的表观活性和比活性的实验测试，制备了 Ln（La、Ce 和 Nd）修饰的 ZIF-67 衍生物电极（Ln/Co/NC）。X 射线光电子能谱数据证实，Ce、Nd 和 La 通过形成不同类型的化学键，在调节衍生 Co/NC 表面原子的配位电子结构方面发挥了各自的作用。电化学（EC）结果证实，Ce 更集中于衍生 Co/NC 电极的表观活性，其在 50 mA cm(-2) 时的过电势最小，而 Nd 对其反应动力学性质的贡献最大，碱性析氢反应过程中的 Tafel 斜率最小。但是，对于析氧反应，所有的 La、Ce 和 Nd 都会降低原始 Co/NC 电极的表观活性。相比之下，La 具有更大的调节 Co/NC 比活性的能力，具有更大的电化学活性表面积归一化电流密度，而 Nd 具有重新建立反应中心性质的最佳能力。这项工作说明了 La、Ce 和 Nd 对 ZIF-67 衍生 Co/NC 电极的表观活性和比活性的影响差异。它将有利于工程 RE 元素修饰的复合电极在 EC 应用中的应用。
