Hydrogen‐Substituted Graphdiyne‐Anchored Ag Single‐Atom Catalyst for Highly Efficient Electrochemical CO ₂ Reduction to CO

Ag single-atom catalysts (SACs) are promising for electrochemical CO₂ reduction reaction (e-CO₂RR) due to their high atom utilization and CO selectivity, yet they often suffer from agglomeration and instability. Here, we employ hydrogen-substituted graphdiyne (HGDY) as a robust support, where abundant alkyne groups strongly coordinate and stabilize atomically dispersed Ag sites. By systematically tuning Ag loading (0.3-10 wt.%), we achieve precise control over active sites and product distribution. The optimized Ag_3.7-HGDY catalyst achieves a remarkable CO Faradaic efficiency (FE_CO) of 98.1% with a turnover frequency (TOF) of 26.5 s^-1, maintaining a FE_CO of ≥97% across a wide potential window (-0.7 to -1.2 V vs RHE). Moreover, Ag loading enables dynamic modulation of CO/H₂ ratios in syngas, highlighting the tunability of the system. This work demonstrates an effective strategy for anchoring noble metals via alkyne coordination, offering a generalizable pathway toward the rational design of stable and scalable single-atom catalysts for CO₂ conversion.