Efficient Electrocatalytic Nitrate Reduction to Ammonia Based on DNA-Templated Copper Nanoclusters

In alkaline solutions, the electrocatalytic conversion of nitrates to ammonia (NH₃) (NO₃RR) is hindered by the sluggish hydrogenation step due to the lack of protons on the electrode surface, making it a grand challenge to synthesize NH₃ at a high rate and selectivity. Herein, single-stranded deoxyribonucleic acid (ssDNA)-templated copper nanoclusters (CuNCs) were synthesized for the electrocatalytic production of NH₃. Because ssDNA was involved in the optimization of the interfacial water distribution and H-bond network connectivity, the water-electrolysis-induced proton generation was enhanced on the electrode surface, which facilitated the NO₃RR kinetics. The activation energy (E_a) and in situ spectroscopy studies adequately demonstrated that the NO₃RR was exothermic until NH₃ desorption, indicating that, in alkaline media, the NO₃RR catalyzed by ssDNA-templated CuNCs followed the same reaction path as the NO₃RR in acidic media. Electrocatalytic tests further verified the efficiency of ssDNA-templated CuNCs, which achieved a high NH₃ yield rate of 2.62 mg h^-1 cm^-2 and a Faraday efficiency of 96.8% at -0.6 V vs reversible hydrogen electrode. The results of this study lay the foundation for engineering catalyst surface ligands for the electrocatalytic NO₃RR.