通过拟单晶扫描电化学池显微镜研究银上析氢反应动力学

doi:10.1016/S1872-2067(22)64158-5

摘要/Abstract

摘要：

阐明电催化剂的结构与其活性之间的关系对于电化学能量转化和储存具有重要的意义. 然而, 催化剂表面结构的异质性为提示真正的构效关系带来了挑战: 催化剂表面通常包括不同的平面, 采用常规方法总体测得的平均催化活性无法代表单一晶体结构的电化学活性. 因此, 本文采用扫描电化学池显微镜(SECCM)结合同位置电子背散射衍射(EBSD)来直接揭示电催化剂局部表面电化学活性与其晶体结构间的关系.

以多晶银表面为例, 通过测量金属银局部表面析氢反应活性与其晶面取向之间的关系来揭示催化活性位点的电化学性质. SECCM和EBSD结果表明, 当晶面靠近{111}时, 析氢反应的电流密度较高; 而靠近{110}晶面时, 则塔菲尔曲线的斜率较低. 同时, 实验发现塔菲尔曲线的斜率随着原子台阶密度的增加而减小. 综上, 本文采用扫描电化学池显微镜与电子背散射衍射相结合的方法, 更精细地分析了金属银局部表面析氢反应活性与其结构间的关系, 为设计制备高活性电催化剂, 以及今后针对其他复杂结构电化学体系的界面动力学研究等提供新的思路.

关键词: 析氢反应动力学, 银, 拟单晶, 扫描电化学池显微镜

Abstract:

Elucidating the structure-activity relationship in electrocatalysis is of fundamental interest for electrochemical energy conversion and storage. However, the heterogeneity in the surface structure of electrocatalysts, including the presence of various facets, poses an analytical challenge in revealing the true structure-activity relationship because the activity is conventionally measured on ensemble, resulting in an averaged activity that cannot be unequivocally associated with a single structural motif. Scanning electrochemical cell microscopy (SECCM) [1] combined with colocalized electron backscatter diffraction (EBSD) offers a direct way to reveal the correlative local electrochemical and structural information. Herein, we measured the hydrogen evolution reaction (HER) activity on Ag and its dependence on the crystal orientation. From the combined EBSD and SECCM mapping, it is found that Ag grains closer to {111} show a higher exchange current density, while those closer to {110} show a lower Tafel slope. The Tafel slope is also found to decrease with the step density increase. The ability to measure the electrocatalytic activity under a high mass-transfer rate allows us to reveal the activity difference at a high current density (up to 200 mA/cm²). The approach reported here can be expanded to other systems to reveal the nature of active sites of electrocatalysis

Key words: Kinetics of hydrogen evolution reaction, Ag, Pseudo-single-crystal, Scanning electrochemical cell, microscopy

王雨菲, 李明阳, 任航. 通过拟单晶扫描电化学池显微镜研究银上析氢反应动力学[J]. 催化学报, 2022, 43(12): 3170-3176.

Yufei Wang, Mingyang Li, Emma Gordon, Hang Ren. Mapping the kinetics of hydrogen evolution reaction on Ag via pseudo-single-crystal scanning electrochemical cell microscopy[J]. Chinese Journal of Catalysis, 2022, 43(12): 3170-3176.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64158-5

https://www.cjcatal.com/CN/Y2022/V43/I12/3170

图/表 6

Scheme 1. Schematic of pseudo-single-crystal measurement of HER activity on polycrystalline Ag. This approach is based on the colocalization of SECCM (left) and EBSD measurements (right).

Fig. 1. (a) Typical local SECCM voltammograms at three different grains on a polycrystalline Ag. These locations are labeled in (c). Solution: 10 mmol/L HClO4. Scan rate: 0.5 V/s. (b) Colocalized SEM image showing the scanned area. White spots indicate the SECCM droplet footprint after the SECCM scan. Local current density map for HER at ?0.75 V (c) and ?0.95 V (d) vs. RHE. (e) Colocalized map of grained-averaged crystal orientation obtained from EBSD. The black lines indicate the high-angle grain boundaries, and the yellow lines indicate the twin boundaries. The averaged crystal orientation of each grain is shown on the standard stereographic triangle, i.e., inverse pole figure. (IPF).

Fig. 2. (a) Example Tafel plots of HER at three different grains. The exact locations are labeled by white square boxes. (b) Map of local Tafel slope (η). The red dash lines represent the grain boundaries. (c) Map of local exchanged current density (j0). (d) Colocalized SEM image showing the footprints of the scanned locations. (e) Colocalized map of grained-averaged crystal orientation obtained from EBSD. The averaged crystal orientation of each grain is shown on the IPF.

Fig. 3. Grain-averaged current density at ?0.75 V (vs. RHE) (a) and ?0.95 V (vs. RHE) (b) plotted on the IPF.

Fig. 4. (a) Grain-averaged exchange current density at ?0.75 V (vs. RHE) as a function of crystal orientation. (b) Grain-averaged Tafel slope as a function of crystal orientation. The positions of the dots on the IPF represents the crystal orientation, while the colors represent current density in (a) and Tafel slope in (b).

Fig. 5. (a) Tafel slope vs step density. r = ?0.47. (b) Log exchange current density (j0) vs. step density. r = 0.13. The calculation of step density is shown in SI section 9.

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