Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO₂ reduction reaction (CO₂RR), whereas the behavior is by far superficially understood. Here, we report that CO₂ accessibility results in a universal self-adaptive structural reconstruction from Cu₂O to Cu@Cu_xO composites, ending with feeding gas-dependent microstructures and catalytic performances. The CO₂-rich atmosphere favors reconstruction for CO₂RR, whereas the CO₂-deficient one prefers that for hydrogen evolution reaction. With the assistance of spectroscopic analysis and theoretical calculations, we uncover a CO₂-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 C₂H₄. An inverse correlation between durability and FE_CO/FE_C2H4 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 Cu₂O nanospheres for durable and selective CO₂RR electrolysis in producing C₂H₄. 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 CO₂ 还原反应 （CO₂RR） 的催化性能中起着关键作用，而到目前为止，人们对这种行为的理解还很肤浅。在这里，我们报道了 CO₂ 可及性导致从 Cu₂O 到 Cu@Cu_xO 复合材料的通用自适应结构重建，最终以馈送气体依赖性微观结构和催化性能结束。富含 CO₂ 的大气有利于 CO₂RR 的重建，而缺乏 CO₂ 的大气有利于析氢反应。在光谱分析和理论计算的帮助下，我们通过鉴定由 *CO 中间体稳定的抗还原但催化活性富 Cu（I） 非晶层，揭示了 CO₂ 诱导的钝化行为。此外，我们发现额外的 CO 生产对于 C₂H₄ 的稳健生产是必不可少的。揭示了耐久性与 FE_CO/FE_C2H4 之间的负相关关系，表明涉及在 Cu（I） 位点吸收 *CO 中间体的自稳定过程对于持久电解至关重要。在这一见解的指导下，我们设计了空心 Cu₂O 纳米球，用于耐用和选择性的 CO₂RR 电解生产 C₂H₄。我们的工作认识到以前被忽视的钝化重建和自稳定行为，并强调了当地大气在调节重建和催化过程中的关键作用。