Carbon dioxide electrochemical reduction reaction (CO₂RR) with proton-electron pair delineates an intriguing prospect for converting CO₂ to useful chemicals. Here by means of first-principle computations, the geometric constructions, electronic structures, and CO₂RR catalytic performance of graphdiyne with single adsorbed alkali metal atoms (AM@GDY) are systematically investigated. The calculated results validate that the AM@GDY complexes possess excellent stability. The catalytic performance is correlated with the size of alkali metal ions. The adsorption free energies of CO₂ on AM@GDY surfaces show that the Li@GDY and Na@GDY can spontaneously capture CO₂ molecules. The interactions between *OCHO specie and AM@GDY are stronger than that between *COOH and AM@GDY, which can promote the CO₂ reduction to HCOOH. The AM@GDY complexes could efficiently convert CO₂ into HCOOH with high-selectivity, and the limiting potentials are −0.56 V on Li@GDY and −0.16 V on Na@GDY monolayers. The present findings not only highlight the importance of AM@GDY for CO₂ electroreduction but also indicate that they are potentially single-atom electrocatalysts.

带有质子-电子对的二氧化碳电化学还原反应（CO ₂ RR）勾勒了将CO ₂转化为有用化学物质的迷人前景。在此，通过第一性原理计算，系统地研究了具有单吸附碱金属原子（AM @ GDY）的石墨二炔的几何结构，电子结构和CO ₂ RR催化性能。计算结果验证了AM @ GDY配合物具有优异的稳定性。催化性能与碱金属离子的大小有关。CO ₂在AM @ GDY表面的吸附自由能表明Li @ GDY和Na @ GDY可以自发捕获CO ₂分子。* OCHO物种与AM @ GDY之间的相互作用比* COOH与AM @ GDY之间的相互作用更强，这可以促进CO ₂还原为HCOOH。AM @ GDY络合物可以高选择性高效地将CO ₂转化为HCOOH，Li @ GDY单层的极限电势为-0.56 V，Na @ GDY单层的极限电势为-0.16V。目前的发现不仅突出了AM @ GDY对于CO ₂电还原的重要性，还表明它们是潜在的单原子电催化剂。