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5.3.2 Scientific challenges It would be highly convenient to use metal electrodes in aqueous electrolytes to catalyse N2 re- duction, capitalising on the deep understanding from other reactions. However, density functional theory (DFT) calculations suggest a fundamental showstopper: the bond strength of any given metal surface to hydrogen linearly correlates to that of nitrogen, as shown in Figure 5.5a. This leads to the poisoning of metal surfaces by hydrogen, preventing the adsorption and subsequent reduction of N2 and leading to poor NH3 selectivity as illustrated in Figure 5.5b [17]. Favouring N2 reduction over H2 evolution requires a surface that circumvents this scaling relation. Moreover, additional scaling relations between N-containing adsorbed intermediates of N2 reduction suggest huge overpotentials for the reaction, as shown in Figure 5.6. The theoretical results in Figures 5.5 and 5.6 provide basis for the incredibly low or negligible concentrations of NH3 reported, thus far, on metal surfaces in aqueous electrolytes and the significant overpotentials required to achieve them. Figure 5.5: a) Linear correlation between potential required to drive first charge transfer step in N2 reduction versus first step of H2 evolution on metal surfaces in aqueous electrolyte. Data from reference [17]. b) Illustration of how poisoning by hydrogen prevents N2 adsorption and subsequent reduction, thereby yielding poor selectivity to ammonia. 5.3.3 Future research needs Below we propose future research needs that are critical to overcoming the aforementioned scientific challenges associated with electrochemical N2 reduction. Adoption of standardised test protocols for N2 electroreduction and benchmark exist- ing literature Given that many reports of electrochemical ammonia production in the current literature are tenta- tive at best, the research community needs to immediately work towards adopting standardised test 55PDF Image | sustainable production of fuels and chemicals
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