Electrocatalytic Hydrogenation Boosts Reduction of Nitrate to Ammonia over Single-Atom Cu with Cu(I)-N3C1 Sites

Abstract

The conversion of nitrate to ammonia can serve two important functions: mitigating nitrate pollution and offering a low energy intensity pathway for ammonia synthesis. Conventional ammonia synthesis from electrocatalytic nitrate reduction reactions (NO₃RR) is often impeded by incomplete nitrate conversion, sluggish kinetics, and the competition of hydrogen evolution reactions. Herein, atomic Cu sites anchored on micro-/mesoporous nitrogen-doped carbon (Cu MNC) with fine-tuned hydrophilicity, micro-/mesoporous channels, and abundant Cu(I) sites were synthesized for selective nitrate reduction to ammonia, achieving ambient temperature and pressure hydrogenation of nitrate. Laboratory experiments demonstrated that the catalyst has an ammonia yield rate per active site of 5466 mmol g_Cu^-1 h^-1 and transformed 94.8% nitrate in wastewater containing 100 mg-N L^-1 to near drinking water standard (MCL of 5 mg-N L^-1) at -0.64 V vs RHE. Extended X-ray absorption fine structure (EXAFS) and theoretical calculations showed that the coordination environment of Cu(I) sites (Cu(I)-N₃C₁) localizes the charge around the central Cu atoms and adsorbs *NO₃ and *H onto neighboring Cu and C sites with balanced adsorption energy. The Cu(I)-N₃C₁ moieties reduce the activation energy of rate-limiting steps (*HNO₃ → *NO₂, *NH₂ → *NH₃) compared with conventional Cu(II)-N₄ and lead to a thermodynamically favorable process to NH₃. The as-prepared electrocatalytic cell can run continuously for 84 h (14 cycles) and produce 21.7 mg_NH3 with only 5.64 × 10^-3 kWh energy consumption, suitable for decentralized nitrate removal and ammonia synthesis from nitrate-containing wastewater.

Keywords: ammonia synthesis; copper; electrocatalytic nitrate reduction; hydrogenation; single-atom catalysts.