Boosting electrochemical coupling of N reduction and biomass oxidation via COF-derived N,P,S-multicoordinated porous carbon with Pt active centers.

The electrochemical nitrogen reduction reaction (eNRR) is a sustainable pathway for ammonia synthesis, yet it faces challenges in selectivity and efficiency. Herein, we report a catalyst characterized by the uniform anchoring of Pt single-atom centers within a nitrogen, phosphorus, sulfur, and carbon (NPSC) multiligand framework, thereby maximizing the advantages of the Pt noble metal and significantly enhancing the eNRR performance. In this catalyst, sulfur-modulated anchoring of the Pt center induces ligand-to-metal charge transfer (LMCT), primarily leveraging the strong interaction between the Pt 4f band and the S 2p orbitals to activate and protonate N effectively. Key findings include an ammonia yield rate (R) of 93.97μg h mgcat and a Faradaic efficiency (FE) of 46.64 % at - 0.30 V vs RHE. Furthermore, advanced flow cell technology improves material transfer efficiency, achieving an R of 326.87μg h mgcat, outperforming many previously reported materials. Moreover, coupling eNRR with the oxidation of 5-hydroxymethylfurfural (HMFOR) enables the concurrent production of green ammonia and high-value chemicals. In situ Raman spectroscopy identifies the -NH group as a crucial intermediate, while Density functional theory (DFT) calculations reveal that the Pt-NPSC catalyst lowers the activation energy for N adsorption and activation. These findings highlight the critical role of innovative catalyst design and device optimization in advancing sustainable ammonia synthesis and provide valuable insights for improving eNRR performance.