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Figure 5.2: a) Ammonia synthesis rate as a function of nitrogen adsorption energy and N2 dissociation barrier with energetics for FCC/HCP metal step sites and scaling line. Shaded area shows the theoretical limit since the activation barrier (Ea) must always be positive. (b) Rate shown as a function of the nitrogen adsorption energy, utilizing that EN−N is a linear function of EN for the considered surfaces. Reproduced with permission from [5]. It should also be noted that operating at lower temperatures may lead to new catalyst chal- lenges. Specifically, special attention needs to be given to catalyst passivation and poisoning by oxygen and other contaminants at low temperatures. 5.3 Electrochemical N2 reduction 5.3.1 State of the art Electrochemical ammonia synthesis is a very nascent tech- nology compared to its thermal counterpart. The concept is illustrated in Figure 5.3 where water is oxidized at the anode, providing protons and electrons to reduce nitrogen at the cathode. A large number of recent research pa- pers have been dedicated to electrochemical N2 reduction; however, the reported concentration of NH3 ranges from the PPB to the PPM level, as described by Andersen et al. and references therein [8]. At such low concentrations, it is challenging to distinguish between ammonia produced from N2 and ammonia produced from adventitious nitro- gen. The only reliable means of verifying N2 reduction is to employ isotope labelling and confirm a quantitative agreement between the ammonia derived from 15N2 and Figure 5.3: Ammonia-producing electrolyzer run- ning on renewable energy. O2 evolution occurs at the anode: 2H2O → O2 + 4H+ + 4e−. The inset shows an electrocatalyst nanoparticle at the cath- ode, where N2 reduction takes place: N2 + 6H+ + 6e− → 2NH3. Schematic illustration by Cristofaro Salvato. 53PDF Image | sustainable production of fuels and chemicals
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