Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3

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Science  08 Aug 2014:
Vol. 345, Issue 6197, pp. 637-640
DOI: 10.1126/science.1254234

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Taking carbon out of the ammonial recipe

The reaction used to make ammonia for synthetic fertilizer requires hydrogen. Nowadays, that hydrogen is stripped from methane, creating CO2 as a by-product. Licht et al. demonstrate a relatively efficient electrochemical process in which water and nitrogen react directly to form ammonia. The approach removes the need for an independent hydrogen generation step. The process takes place in molten hydroxide salt and requires a nanostructured iron oxide–derived catalyst. Although the catalyst suspension is currently only stable for a few hours, the protocol points to a way to produce ammonia from purely renewable resources.

Science, this issue p. 637


The Haber-Bosch process to produce ammonia for fertilizer currently relies on carbon-intensive steam reforming of methane as a hydrogen source. We present an electrochemical pathway in which ammonia is produced by electrolysis of air and steam in a molten hydroxide suspension of nano-Fe2O3. At 200°C in an electrolyte with a molar ratio of 0.5 NaOH/0.5 KOH, ammonia is produced at 1.2 volts (V) under 2 milliamperes per centimeter squared (mA cm−2) of applied current at coulombic efficiency of 35% (35% of the applied current results in the six-electron conversion of N2 and water to ammonia, and excess H2 is cogenerated with the ammonia). At 250°C and 25 bar of steam pressure, the electrolysis voltage necessary for 2 mA cm−2 current density decreased to 1.0 V.

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