Mapping the kinetics of hydrogen evolution reaction on Ag via pseudo-single-crystal scanning electrochemical cell microscopy

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64158-5

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

Figures/Tables 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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