Fang-Fang Li

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

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 An electrochemical route offers preliminary prospects for making the ammonia in fertilizer purely from renewable resources. 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.

One-Pot Synthesis of Carbon Nanofibers from CO2

Carbon nanofibers, CNFs, due to their superior strength, conductivity, flexibility, and durability have great potential as a material resource but still have limited use due to the cost intensive complexities of their synthesis. Herein, we report the high-yield and scalable electrolytic conversion of atmospheric CO2 dissolved in molten carbonates into CNFs. It is demonstrated that the conversion of CO2 → CCNF + O2 can be driven by efficient solar, as well as conventional, energy at inexpensive steel or nickel electrodes. The structure is tuned by controlling the electrolysis conditions, such as the addition of trace transition metals to act as CNF nucleation sites, the addition of zinc as an initiator and the control of current density. A less expensive source of CNFs will facilitate its adoption as a societal resource, and using carbon dioxide as a reactant to generate a value added product such as CNFs provides impetus to consume this greenhouse gas to mitigate climate change.

Advances in Understanding the Mechanism and Improved Stability of the Synthesis of Ammonia from Air and Water in Hydroxide Suspensions of Nanoscale Fe2O3

We report a mechanism of electrochemical ammonia (NH3) production via an iron intermediate in which H2 and NH3 are cogenerated by different electron-transfer pathways. Solar thermal can contribute to the energy to drive this synthesis, resulting in a STEP, solar thermal electrochemical process, for NH3. Enhancements are presented to this carbon dioxide (CO2)-free synthesis, which uses suspensions of nano-Fe2O3 in high-temperature hydroxide electrolytes at nickel and Monel electrodes. In a 200 °C molten eutectic Na(0.5)K(0.5)OH electrolyte, the 3 Faraday efficiency per mole of synthesized NH3, η(NH3), increases with decreasing current density, and at j(electrolysis) = 200, 25, 2, and 0.7 mA cm(-2), η(NH3) = 1%, 7%, 37%, and 71%, respectively. At 200 mA cm(-2), over 90% of applied current drives H2, rather than NH3, formation. Lower temperature supports greater electrolyte hydration. At 105 °C in the hydrated Na(0.5)K(0.5)OH electrolyte, η(NH3) increases and then is observed to be highly stable at η(NH3) = 24(+2)%.

Sungas Instead of Syngas: Efficient Coproduction of CO and H2 with a Single Beam of Sunlight.

The electrolytic coproduction of CO and H2 is achieved from air, water, and a single beam of sunlight rather than from fossil fuels. H2 and CO cosynthesis is driven by a single concentrator photovoltaic to simultaneously drive molten hydroxide and molten carbonate electrolyses. The carbon neutral process captures carbon without the need for the preconcentration of atmospheric carbon dioxide.