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

ABSTRACT Ag single‐atom catalysts (SACs) are promising for electrochemical CO 2 reduction reaction (e‐CO 2 RR) 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/H 2 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 CO 2 conversion.