Wang Hui, Mandemaker Laurens D B, de Ruiter Jim, Yu Xiang, van der Stam Ward, Weckhuysen Bert M
Inorganic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry, Department of Chemistry, Faculty of Science, Utrecht University, Universiteitsweg 99, 3584CG, Utrecht, The Netherlands.
Angew Chem Int Ed Engl. 2025 Apr 11;64(16):e202424530. doi: 10.1002/anie.202424530. Epub 2025 Feb 11.
Studies on the catalyst restructuring during the electrochemical CO reduction reaction (eCORR) are limited and mostly focused on Cu (001) or (111) single crystals as model systems. A comprehensive overview of the dynamic restructuring of different Cu facets is lacking. Here, we first reveal the facet-dependent restructuring of polycrystalline Cu electrodes through electron backscatter diffraction (EBSD) and identical grain atomic force microscopy (AFM). This combined analysis provides new insights into the evolution of crystal domains (EBSD) and surface topography (AFM) at varying conditions (e.g., applied potential and oxidative-reductive pulses). The statistic slope distribution function was applied to study the restructuring asymmetry on five Cu facets (i.e., planar vs. atom stepped). We find that planar Cu (001) shows a square-shaped morphology after eCORR with 4-fold asymmetry restructuring behavior, while triangular features dominate on Cu (111), evidenced by surface changes with 3-fold asymmetry. 2-fold restructuring is observed for Cu (114), (212), and (124) with atom steps, resulting in forming elongated structures. Therefore, the surface restructuring is dominated by the asymmetry of its facet lattice structure (i.e., planar vs. atom-stepped). This work underscores the potential of combining techniques to elucidate the relationship between surface restructuring and crystal facets on different length scales.
关于电化学CO还原反应（eCORR）过程中催化剂重构的研究有限，且大多集中在Cu(001)或(111)单晶作为模型体系。目前缺乏对不同Cu晶面动态重构的全面概述。在此，我们首先通过电子背散射衍射（EBSD）和相同晶粒原子力显微镜（AFM）揭示了多晶Cu电极的晶面依赖性重构。这种联合分析为不同条件下（如施加电位和氧化还原脉冲）晶体畴（EBSD）和表面形貌（AFM）的演变提供了新的见解。应用统计斜率分布函数研究了五个Cu晶面（即平面与原子台阶面）上的重构不对称性。我们发现，eCORR后平面Cu(001)呈现方形形态，具有四重不对称重构行为，而三角形特征在Cu(111)上占主导，表面变化呈现三重不对称性。对于具有原子台阶的Cu(114)、(212)和(124)，观察到二重重构，形成细长结构。因此，表面重构由其晶面晶格结构的不对称性（即平面与原子台阶面）主导。这项工作强调了结合技术以阐明不同长度尺度上表面重构与晶面之间关系的潜力。
