The poor stability of heterogenized nickel phthalocyanine (NiPc) has hindered its application as a desirable catalyst for electrocatalytic carbon dioxide reduction. Herein, the electrocatalytic stability of heterogenized NiPc on nitrogen-doped hollow carbon nanospheres (NiPc@NHCSs) can be optimized via mediating NiPc into Ni-NC moiety (Ni-NC/NHCSs-Y) to construct a stable Ni catalytic unit. Different from the poor activity of NiPc@NHCSs (CO Faradaic efficiency, ${\mathit{FE}}_{CO}$< 80%, stability < 1200 s), the optimal catalyst (Ni-NC/NHCSs-600) with unsaturated Ni-N₃ nitrogen-vacancy structure, displays ${\mathit{FE}}_{CO}$ of 98.57% and CO turnover frequency of 3.75 s⁻¹ at − 0.87 V vs. RHE, and stable operation over 14 h (−0.82 V vs. RHE). The stabilization mechanism and the temperature effect on the structure-activity relationship are systematically explored, which successfully steers the design of stable Ni-NC catalytic unit on different carbon substrate, while a zinc-CO₂ rechargeable battery is constructed, displaying a peak power density of 0.64 mW cm⁻² and ${\mathit{FE}}_{\mathit{CO}}$ of 91.45%.

异质化镍酞菁（NiPc）稳定性差，阻碍了其作为电催化二氧化碳还原催化剂的应用。在此，可以通过将NiPc介导到Ni-NC部分（Ni-NC/NHCSs- Y ）中来优化异质NiPc在氮掺杂中空碳纳米球（NiPc@NHCSs）上的电催化稳定性，以构建稳定的Ni催化单元。不同于 NiPc@NHCSs 的活性差（CO 法拉第效率，${\mathit{FE}}_{C○}$< 80%, 稳定性 < 1200 s), 具有不饱和 Ni-N ₃氮空位结构的最佳催化剂 (Ni-NC/NHCSs-600), 展示${\mathit{FE}}_{C○}$为 98.57%，CO 周转频率为 3.75 s ^-1在 - 0.87 V vs。RHE，并在 14 小时内稳定运行（-0.82 V与RHE）。系统地探讨了稳定机制和温度对构效关系的影响，成功指导了在不同碳基底上稳定的 Ni-NC 催化单元的设计，同时构建了具有峰值功率密度的锌-CO ₂可充电电池0.64 mW cm ^-2和${\mathit{FE}}_{\mathit{一氧化碳}}$91.45%。