Abstract The rational design of asymmetrically coordinated dual‐atom catalysts (DACs) offers new opportunities to overcome intrinsic limitations in selective multi‐electron electrochemical reactions. Here, we present a general synthetic strategy that exploits high‐energy metal‐organic frameworks (EMOFs, such as nitrogen‐rich MOFs) as versatile precursors to construct a diverse library of atomically dispersed and structurally asymmetric DACs. By leveraging the exothermic decomposition and gas‐releasing nature of Zn‐based EMOFs such as Zn(C 2 H 2 N 3 ) 2 (1,2,3‐triazolate, MET‐6), we achieve the in situ formation of porous nitrogen‐doped carbon frameworks embedding various Zn─M (M = Co, Fe, Mn, Pd, Pt, Ni, Ru) dual‐atom sites with tailored asymmetric coordination environments. This far‐from‐equilibrium route enables atomic dispersion while steering the formation of non‐centrosymmetric metal sites that are otherwise challenging to access via conventional thermal treatments. Across the DACs library, the Zn─Co/NC member stands out for electrochemical nitrate reduction (NO 3 RR), delivering a Faradaic efficiency of 98.95% toward NH 3 at −0.4 V. In situ X‐ray absorption spectroscopy (XAS) and density functional theory calculations reveal that the asymmetric N 3 Zn─CoN 2 configuration enhances electronic coupling between the two metal centers, optimizes *NOH adsorption, and lowers the activation barrier for key intermediates. This work establishes a broadly applicable route to asymmetric DACs and provides a platform for tailoring active‐site configurations to diverse electrochemical transformations.
Wei et al. (Sat,) studied this question.