Temperature‐Induced Low‐Coordinate Ni Single‐Atom Catalyst for Boosted CO₂ Electroreduction Activity

Abstract Single‐atom catalysts (SACs) exhibit remarkable potential for electrochemical reduction of CO₂ to value‐added products. However, the commonly pursued methods for preparing SACs are hard to scale up, and sometimes, lack general applicability because of expensive raw materials and complex synthetic procedures. In addition, the fine tuning of coordination environment of SACs remains challenging due to their structural vulnerability. Herein, a simple and universal strategy is developed to fabricate Ni SACs with different nitrogen coordination numbers through one‐step pyrolysis of melamine, Ni(NO₃)∙6H₂O, and polyvinylpyrrolidone at different temperatures. Experimental measurements and theoretical calculations reveal that the low‐coordinate Ni SACs exhibit outstanding CO₂ reduction performance and stability, achieving a Faradic efficiency (FE_CO) of 98.5% at −0.76 V with CO current density of 24.6 mA cm⁻², and maintaining FE_CO of over 91.0% at all applied potential windows from −0.56 to −1.16 V, benefiting from its coordinatively unsaturated structure to afford high catalytic activity and low barrier for the formation of *COOH intermediate. No significant performance degradation is observed over 50 h of continuous operation. Additionally, several other metallic single‐atom catalysts are successfully prepared by this synthetic method, demonstrating the universality of this strategy.