p–d Orbital Hybridization in Ag‐based Electrocatalysts for Enhanced Nitrate‐to‐Ammonia Conversion

Abstract Considering the substantial role of ammonia, developing highly efficient electrocatalysts for nitrate‐to‐ammonia conversion has attracted increasing interest. Herein, we proposed a feasible strategy of p–d orbital hybridization via doping p‐block metals in an Ag host, which drastically promotes the performance of nitrate adsorption and disassociation. Typically, a Sn‐doped Ag catalyst (SnAg) delivers a maximum Faradaic efficiency (FE) of 95.5±1.85 % for NH 3 at −0.4 V vs. RHE and reaches the highest NH 3 yield rate to 482.3±14.1 mg h −1 mg cat. −1 . In a flow cell, the SnAg catalyst achieves a FE of 90.2 % at an ampere‐level current density of 1.1 A cm −2 with an NH 3 yield of 78.6 mg h −1 cm −2 , during which NH 3 can be further extracted to prepare struvite as high‐quality fertilizer. A mechanistic study reveals that a strong p–d orbital hybridization effect in SnAg is beneficial for nitrite deoxygenation, a rate‐determining step for NH 3 synthesis, which as a general principle, can be further extended to Bi‐ and In‐doped Ag catalysts. Moreover, when integrated into a Zn‐nitrate battery, such a SnAg cathode contributes to a superior energy density of 639 Wh L −1 , high power density of 18.1 mW cm −2 , and continuous NH 3 production.