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The exceptional electronic properties and potential applications of black phosphorus (BP) have garnered significant interest in the fields of electrochemical catalysis and energy storage. However, its poor environmental stability severely hampers its practical use. In this study, an innovative strategy is proposed to protect fresh black phosphorene (BPene) against oxidation by adsorbing or weakly bonding aluminum ions (Al3+) onto its surface, while facilitating their self‐removal under operating conditions. By leveraging Al3+‐protected black phosphorene (Al‐BPene) as a catalyst for the electrocatalytic reduction of nitrogen to ammonia (NH3), the effectiveness of this removable Al3+‐protected strategy is demonstrated. Quantitative analysis reveals that Al‐BPene maintains structural and compositional stability for over 7 days under ambient conditions, while the Al3+ can be readily eliminated through self‐desorption or dissolution in the electrolyte. With highly active sites pre‐protected, Al‐BPene exhibits a striking NH3 yield rate of 55.1 µg h−1 mg cat−1 and a Faradaic efficiency (FE) of 66.5% in alkaline media, as exemplified by the representative application example. Moreover, it is found that the prepared Al‐BPene can tolerate a thermal environment, and a higher NH3 yield rate of 75 µg h−1 mg cat−1 at 60 °C is recorded. Undoubtedly, these findings pave the way for broader applications of BPene. [ABSTRACT FROM AUTHOR]

The current industrial synthesis of ammonia involves an energy‐intensive Haber‐Bosch process, significantly contributing to a massive carbon footprint. An electrochemical synthetic pathway for nitrogen fixation has recently garnered significant attention. It allows ammonia production through a green process without generating harmful pollutants. However, due to the robust N≡N bond, the limited nitrogen solubility, and the competing reactions of hydrogen extraction, the synthesis of ammonia by electrochemical nitrogen reduction (e‐NRR) is far from achieving industrialization. The intrinsic properties of the catalyst, the gas‐solid‐liquid interface, and the specific design of reaction system are the key factors that affect e‐NRR performance. Therefore, this review discusses recent efforts in enhancing e‐NRR performance towards ammonia production with regards to catalyst design, reaction interface optimization, and modulation of the reaction system (including lithium mediated ammonia synthesis). Finally, various promising research strategies and remaining tasks are presented. It is anticipated that this review could be beneficial for the further development of highly efficient and selective e‐NRR to ammonia. [ABSTRACT FROM AUTHOR]

Electrocatalytic N2 reduction reaction (NRR) is recognized as a zero‐carbon emission method for NH3 synthesis. However, to date, this technology still suffers from low yield and low selectivity associated with the catalyst. Herein, inspired by the activation of N2 by lithium metal, a highly reactive defective black phosphorene (D−BPene) is proposed as a lithium‐like catalyst for boosting electrochemical N2 activation. Correspondingly, we also report a strategy for producing environmentally stable D−BPene by simultaneously constructing defects and fluorination protection based on topochemical reactions. Reliable performance evaluations show that the fluorine‐stabilized D−BPene can induce a high NH3 yield rate of ≈70 μg h−1 mgcat.−1 and a high Faradaic efficiency of ≈26 % at −0.5 V vs. RHE in an aqueous electrolyte. This work not only exemplifies the first stable preparation and practical application of D−BPene, but also brings a new design idea for NRR catalysts. [ABSTRACT FROM AUTHOR]

The electrocatalytic nitrogen reduction reaction (NRR) to ammonia (NH3) is a highly desirable yet challenging objective because of the competing hydrogen evolution reaction (HER). Herein, a novel electrocatalyst of Sn‐doped black phosphorene (Sn‐BPene) is demonstrated with dramatically improved selectivity for the NRR. The Sn that is added acts as a sacrificial species for the HER to protect the NRR active sites on black phosphorene (BPene). The Sn‐BPene achieves a Faraday efficiency of up to 36.51% and a prominent NH3 yield rate of 26.98 µg h–1 mgcat–1 at a relatively low overpotential. Density functional theory calculations prove that the adsorption sites of H2O and N2 are separated after doping with Sn, with H2O adsorbing preferentially onto the Sn sites and N2 onto the NRR active sites of BPene, leading to high selectivity. [ABSTRACT FROM AUTHOR]

Electrochemical nitrogen reduction reaction can be adopted to generate renewable ammonia. That is recognized as a sustainable alternative to the Haber-Bosch process. However, the limited electrocatalytic activity remains the primary obstacle against viable application of the electrocatalytic ammonia fixation. Herein, a biomimetic three-dimensional NiCoP/CoMoP/Co(Mo 3 Se 4) 4 @C/NF electrocatalyst is designed to have excellent NRR performance with an NH 3 yield rate of 24.54 μg h−1 cm−2 and Faradaic efficiency of 23.15%. Based on the experimental and theoretical results, NiCoP/CoMoP/Co(Mo 3 Se 4) 4 @C/NF electrocatalyst perfectly simulates the structural characteristics of biological nitrogenase, where Co(Mo 3 Se 4) 4 acts as the major active center while NiCoP and CoMoP contribute to controlling the electron transfer during NRR. Additionally, the coexistence of the three different heterojunction interfaces induces more effective electronic structure modulation compared with the single interface, thereby optimizing the reaction energy barrier of intermediates. This work has developed a synergistic strategy to boost the reaction kinetics via introducing multiple heterojunction interfaces. [Display omitted] • NiCoP/CoMoP/Co(Mo 3 Se 4) 4 @C/NF have excellent N 2 reduction performance. • NiCoP/CoMoP/Co(Mo 3 Se 4) 4 @C/NF simulates the structure of nitrogenase. • Multiple heterojunction interfaces induce effective electron redistribution. • Multiple heterojunction interfaces optimize the reaction energy barrier. [ABSTRACT FROM AUTHOR]