Dinitrogen Reduction Coupled with Methanol Oxidation for Low Overpotential Electrochemical NH 3 Synthesis Over Cobalt Pyrophosphate as Bifunctional Catalyst.

Electrochemical dinitrogen (N 2 ) reduction to ammonia (NH 3 ) coupled with methanol electro-oxidation is presented in the current work. Here, methanol oxidation reaction (MOR) is proposed as an alternative anode reaction to oxygen evolution reaction (OER) to accomplish electrons-induced reduction of N 2 to NH 3 at cathode and oxidation of methanol at anode in alkaline media thereby reducing the overall cell voltage for ammonia production. Cobalt pyrophosphate micro-flowers assembled by nanosheets are synthesized via a surfactant-assisted sonochemical approach. By virtue of structural and morphological advantages, the maximum Faradaic efficiency of 43.37% and NH 3 yield rate of 159.6 µg h -1 mg ca -1 is achieved at a potential of -0.2 V versus RHE. The proposed catalyst is shown to also exhibit a very high activity (100 mA mg -1 at 1.48 V), durability (2 h) and production of value-added formic acid at anode (2.78 µmol h -1 mg cat -1 and F.E. of 59.2%). The overall NH 3 synthesis is achieved at a reduced cell voltage of 1.6 V (200 mV less than NRR-OER coupled NH 3 synthesis) when OER at anode is replaced with MOR and a high NH 3 yield rate of 95.2 µg h -1 mg cat -1 and HCOOH formation rate of 2.53 µmol h -1 mg -1 are witnessed under full-cell conditions.