Ma Yi, Yang Qi, Qi Jun, Zhang Yong, Gao Yuliang, Zeng You, Jiang Na, Sun Ying, Qu Keqi, Fang Wenhui, Li Ying, Lu Xuejun, Zhi Chunyi, Qiu Jieshan
State Key Laboratory of Chemical Resource Engineering, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
Institute of Clean Energy Chemistry, Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials of Liaoning Province, College of Chemistry, Liaoning University, Shenyang 110036, China.
Proc Natl Acad Sci U S A. 2024 Apr 9;121(15):e2319525121. doi: 10.1073/pnas.2319525121. Epub 2024 Apr 2.
The fine regulation of catalysts by the atomic-level removal of inactive atoms can promote the active site exposure for performance enhancement, whereas suffering from the difficulty in controllably removing atoms using current micro/nano-scale material fabrication technologies. Here, we developed a surface atom knockout method to promote the active site exposure in an alloy catalyst. Taking CuPd alloy as an example, it refers to assemble a battery using CuPd and Zn as cathode and anode, the charge process of which proceeds at about 1.1 V, equal to the theoretical potential difference between Cu/Cu and Zn/Zn, suggesting the electricity-driven dissolution of Cu atoms. The precise knockout of Cu atoms is confirmed by the linear relationship between the amount of the removed Cu atoms and the battery cumulative specific capacity, which is attributed to the inherent atom-electron-capacity correspondence. We observed the surface atom knockout process at different stages and studied the evolution of the chemical environment. The alloy catalyst achieves a higher current density for oxygen reduction reaction compared to the original alloy and Pt/C. This work provides an atomic fabrication method for material synthesis and regulation toward the wide applications in catalysis, energy, and others.
通过原子级去除非活性原子对催化剂进行精细调控,可促进活性位点暴露以提高性能,然而目前的微纳尺度材料制备技术难以可控地去除原子。在此,我们开发了一种表面原子敲除方法来促进合金催化剂中的活性位点暴露。以铜钯合金为例,该方法是指用铜钯和锌分别作为阴极和阳极组装电池,其充电过程在约1.1 V下进行,这与铜/铜和锌/锌之间的理论电位差相等,表明铜原子发生电驱动溶解。去除的铜原子量与电池累积比容量之间的线性关系证实了铜原子的精确敲除,这归因于固有的原子-电子-容量对应关系。我们观察了不同阶段的表面原子敲除过程,并研究了化学环境的演变。与原始合金和铂碳相比,该合金催化剂在氧还原反应中实现了更高的电流密度。这项工作为材料合成和调控提供了一种原子制造方法,有望在催化、能源等领域广泛应用。