Nitrogen‐Rich MOF‐Material‐Derived Metal Dual‐Atom Platforms for Efficient Electrochemical Nitrate Reduction

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(C₂H₂N₃)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 (NO₃RR), delivering a Faradaic efficiency of 98.95% toward NH₃ at -0.4 V. In situ X-ray absorption spectroscopy (XAS) and density functional theory calculations reveal that the asymmetric N₃Zn─CoN₂ 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.