Bridging the Gap in the Mechanistic Understanding of Electrocatalysis via In Situ Characterizations.

Electrocatalysis offers a promising strategy to take advantage of the increasingly available and affordable renewable energy for the sustainable production of fuels and chemicals. Attaining this promise requires a molecular level insight of the electrical interface that can be used to tailor the selectivity of electrocatalysts. Addressing this selectivity challenge remains one of the most important areas in modern electrocatalytic research. In this Perspective, we focus on the use of in situ techniques to bridge the gap in the fundamental understanding of electrocatalytic processes. We begin with a brief discussion of traditional electrochemical techniques, ex situ measurements and in silico analysis. Subsequently, we discuss the utility and limitations of in situ methodologies, with a focus on vibrational spectroscopies. We then end by looking ahead toward promising new areas for the application of in situ techniques and improvements to current methods.

Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles.

Renewable production of ammonia, a building block for most fertilizers, via the electrochemical nitrogen reduction reaction (ENRR) is desirable; however, a selective electrocatalyst is lacking. Here we show that vanadium nitride (VN) nanoparticles are active, selective, and stable ENRR catalysts with an ENRR rate and a Faradaic efficiency (FE) of 3.3 × 10-10 mol s-1 cm-2 and 6.0% at -0.1 V within 1 h, respectively. ENRR with 15N2 as the feed produces both 14NH3 and 15NH3, which indicates that the reaction follows a Mars-van Krevelen mechanism. Ex situ X-ray photoelectron spectroscopy characterization of fresh and spent catalysts reveals that multiple vanadium oxide, oxynitride, and nitride species are present on the surface and identified VN0.7O0.45 as the active phase in the ENRR. Operando X-ray absorption spectroscopy and catalyst durability test results corroborate this hypothesis and indicate that the conversion of VN0.7O0.45 to the VN phase leads to catalyst deactivation. We hypothesize that only the surface N sites adjacent to a surface O are active in the ENRR. An ammonia production rate of 1.1 × 10-10 mol s-1 cm-2 can be maintained for 116 h, with a steady-state turnover number of 431.