Single-Atom Tailoring of the Electronic Structure of the Conductive Porous Coordination Polymer Enhances Efficient Electrochemical NH₃ Production

Conductive porous coordination polymers (PCPs) and metal–organic frameworks (MOFs) are promising candidates for electrocatalysts and advanced electronic devices. Tailoring the electronic structure of conductive PCPs/MOFs is crucial for achieving specific applications, but it remains challenging. Herein, we introduce a novel approach called the “single-atom” strategy to tailor the electronic structure of conductive PCPs/MOFs to enhance the electrocatalytic performance for the reduction of nitrate to ammonia. By incorporating atomically dispersed Ru 3+ (at a content of about 5% per Co) into semiconducting PCPs, we successfully created a highly efficient PCP-based electrocatalyst named Ru–Co-pyNDI, which exhibits good structural stability and improved electrocatalytic performance. The calculated and experimental results reveal that doping atomically dispersed Ru 3+ into Co-pyNDI induces local structural distortion, resulting in a downshift of the d-band center of the Co, which in turn facilitates the desorption of intermediates. As a result, the Ru–Co-pyNDI catalyst demonstrates superior electrocatalytic performance in NH 3 production compared to other heterogeneous catalysts, achieving a high Faradaic efficiency of about 97% and an ammonia yield rate of 12010 μg h –1 mg cat. –1 (0.28 mmol h –1 cm –2 ) under neutral aqueous conditions.