Interfacial Proton Supply/Filtration Regulates the Dynamics of Electrocatalytic Nitrogen Reduction Reaction: A Perspective

Abstract

As a promising energy carrier, ammonia synthesis by electrocatalytic nitrogen reduction reaction (eNRR) is a promising green and low‐carbon ammonia synthesis strategy that can replace the traditional Haber–Bosch process. However, the development of eNRR processes is mainly severely constrained by competitive hydrogen evolution reaction (HER), and the corresponding strategies to inhibit this adverse side reaction to obtain high eNRR selectivity are still limited. In addition, for this complex reaction involving gas–liquid–solid three‐phase interface and proton/electron transfer, it is great significance to analyze and summarize the existing inhibition HER strategies from the viewpoint of dynamics. In view of this, this work reviews proton supply/filtration regulation strategy in catalytic system, allowing a systematic survey of the literature focusing on interface membrane regulation (inorganic membrane and organic membrane), electrolyte regulation (metal‐mediated strategy and electrolyte ion regulation strategy) and system device design (electrode structure design and electrolytic cell device design). Constructive catalytic system design guidance is also suggested to inhibit hydrogen evolution and improve NH3 selectivity, aiming for scalable and economically feasible applications.

Insight from Boric Acid into Bioskeleton Formation: Inscribed Circle Effect on the Edge-Base Plate Growth

“…Boric acid can serve as both an acceptor and a donor for hydrogen bonding. The boron atom possesses a robust electron-attracting ability for the boric acid molecule, which results in the bonding electron cloud of the oxygen atom in the B–O bond being biased toward the boron atom and less likely interacting with the hydrogen atom in the O–H bond of the alcohol molecule. Consequently, at the 010 crystalline facet of boric acid, the oxygen atom in the alcohol molecule is more stable in the configuration facing the hydrogen atom in the boric acid molecule (Figure S5–S7).…”

Recent Advances in Designing Catalysts and Reaction Systems for Electrochemical Synthesis of Ammonia

“…However, current research has demonstrated that the mechanism of heterogeneous catalytic e‐NRR at the interface remains a subject of debate, with the two main proposed mechanisms being the dissociation mechanism (Figure 2a) and the association mechanism (Figure 2c and 2d). [6a,11] The dissociation mechanism, exemplified by the Haber‐Bosch process, involves breaking the N≡N bond before the hydrogenation reaction, thus necessitating a substantial energy input. Conversely, the e‐NRR processes on various catalyst surfaces predominantly follow the association mechanism, where the N≡N bond breaks simultaneously with the release of the first ammonia molecule.…”

“…[10] Prior to the e-NRR to ammonia process, nitrogen needs to be dissolved into the electrolyte and cross the solid-liquid interface to reach the catalyst surface. [11] Therefore, both the inherent properties of the electrolyte and the microenvironment of the solid-liquid interface also have a great influence on the nitrogen reduction performance. In this concept article, the strategies to enhance the performance of e-NRR to ammonia are summarized and analyzed from three perspectives: the design of catalysts, the modification of reaction interfaces, and the reaction system modulation (Figure 1).…”

“…Facing the above three urgent problems, developing catalysts with high activity and selectivity is essential to enhance performance [10] . Prior to the e‐NRR to ammonia process, nitrogen needs to be dissolved into the electrolyte and cross the solid‐liquid interface to reach the catalyst surface [11] . Therefore, both the inherent properties of the electrolyte and the microenvironment of the solid‐liquid interface also have a great influence on the nitrogen reduction performance.…”

Cu(N2)-Li Battery for Ammonia Synthesis

“…While numerous catalysts for NRR have emerged in aqueous solutions, challenges arise due to the limited solubility, diffusion, and chemical inertness of N 2 , compounded by the presence of the hydrogen evolution side reaction (HER), thereby impeding industrialization efforts. More importantly, some researchers have raised concerns about the potential experimental false positives in water-based systems, as synthesized ammonia could originate from external sources of pollution. − …”