Zhang Chaoran, Gu Yichuan, Jiang Qu, Sheng Ziyang, Feng Ruohan, Wang Sihong, Zhang Haoyue, Xu Qianqing, Yuan Zijian, Song Fang
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai, 200240, People's Republic of China.
Nanomicro Lett. 2024 Nov 19;17(1):66. doi: 10.1007/s40820-024-01568-1.
Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO reduction reaction (CORR), whereas the behavior is by far superficially understood. Here, we report that CO accessibility results in a universal self-adaptive structural reconstruction from CuO to Cu@CuO composites, ending with feeding gas-dependent microstructures and catalytic performances. The CO-rich atmosphere favors reconstruction for CORR, whereas the CO-deficient one prefers that for hydrogen evolution reaction. With the assistance of spectroscopic analysis and theoretical calculations, we uncover a CO-induced passivation behavior by identifying a reduction-resistant but catalytic active Cu(I)-rich amorphous layer stabilized by *CO intermediates. Additionally, we find extra CO production is indispensable for the robust production of CH. An inverse correlation between durability and FE/FE is disclosed, suggesting that the self-stabilization process involving the absorption of *CO intermediates on Cu(I) sites is essential for durable electrolysis. Guided by this insight, we design hollow CuO nanospheres for durable and selective CORR electrolysis in producing CH. Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.
电催化剂的结构重构在一氧化碳还原反应（CORR）的催化性能中起着关键作用，然而到目前为止，这种行为还只是被肤浅地理解。在此，我们报道一氧化碳的可及性导致了从氧化铜到铜@氧化铜复合材料的普遍自适应结构重构，最终形成依赖于进料气体的微观结构和催化性能。富含一氧化碳的气氛有利于CORR的重构，而缺乏一氧化碳的气氛则更有利于析氢反应的重构。借助光谱分析和理论计算，我们通过识别由CO中间体稳定的富铜（I）抗还原但具有催化活性的非晶层，揭示了一氧化碳诱导的钝化行为。此外，我们发现额外的一氧化碳生成对于甲烷的稳定生成是必不可少的。耐久性与法拉第效率/分电流效率之间呈现负相关，这表明涉及CO中间体在铜（I）位点上吸附的自稳定过程对于持久电解至关重要。基于这一认识，我们设计了空心氧化铜纳米球用于在生产甲烷时进行持久且选择性的CORR电解。我们的工作认识到了先前被忽视的钝化重构和自稳定行为，并突出了局部气氛在调节重构和催化过程中的关键作用。
