Electrochemical NH3 Synthesis Research Articles

Regioselective Doping into Atomically Aligned Core–Shell Structures for Electrocatalytic Reduction of Nitrate to Ammonia

AbstractThe electrochemical nitrate reduction reaction (NO3−RR) presents an environmentally friendly approach for efficient NO3− pollutant removal and ammonia (NH3) production, compared to the conventional Haber–Bosch approach. While core/shell engineering has demonstrated its potential in enhancing NO3−RR performance, significant synthetic challenges and limited shell layer modification capabilities impede the exploration of high‐performance NO3−RR core/shell catalysts. Herein, CuCoO/Co(OH)2 core/shell structure via in situ electrochemical activation is synthesized. The catalyst delivers a maximum NH3 Faradaic efficiency (FE) of 94.7% at −0.5 VRHE with excellent durability and selectivity for NH3 over a wide range of potentials in NO3−RR, surpassing the electrocatalytic performance of both undoped shell and core components. The outstanding performance Cu─CoO/Co(OH)2 is ascribed to the enhanced charge transfer, stabilization of key reaction intermediates, and regulation of hydrogen adsorption over Cu‐doped core/shell structure. Furthermore, the assembled Zn−NO3− battery device attains a peak current density exceeding 32 mA cm−2 and an NH3 yield of up to 145.4 µmol h−1 cm−2. The work offers a novel core/shell engineering strategy in electrocatalytic NO3−RR and sheds light on the doping effects on the electrochemical NH3 synthesis.

A high-performance electrocatalyst for sustainable ammonia synthesis via single-atom Ru-embedded Fe2O3 nitrogen-DOPED carbon

Ammonia (NH3) is an important industrial chemical, but the production of NH3 by the conventional Haber-Bosch process consumes large amounts of energy and has a serious environmental impact. Electrochemical nitrogen reduction reaction (NRR) offers a promising green alternative, but challenges remain in developing efficient catalysts. Here, we report the synthesis of single-atom Ru-embedded metal–organic framework-derived Fe2O3 nitrogen-doped carbon (Ru/Fe2O3-NC) materials via plasma-enhanced chemical vapour deposition. Under ambient conditions, the Ru/Fe2O3-NC catalyst exhibited a high NH3 yield rate of 141.18 μg h−1 mgcat.−1 in 0.1 M K2SO4 with a Faraday efficiency (FE) of 48.89 %, which was superior to the pristine Fe2O3-NC catalyst. Online differential electrochemical mass spectrometry (DEMS) analysis confirmed the selective generation of NH3 and no by-product N2H4 was detected. The Ru/Fe2O3-NC catalyst also showed remarkable stability during prolonged electrolysis. This work demonstrates the synergistic effect of incorporating single-atomic Ru in the Fe2O3-NC framework and provides a new platform for the development of advanced catalysts for the efficient and sustainable electrochemical synthesis of NH3.

Enhanced nitrogen electroreduction to ammonia activities on Sb2S3 electrocatalyst by sulfur defects coupled with carbon doping

Exploiting effective, robust while cheap catalysts for the nitrogen reduction reaction (NRR) is of great significance in the scalability and renewability of electrochemical NH3 synthesis. Herein, a synergetic strategy of C dopants and S vacancies was employed into Sb2S3 (marked as C-Sb2S3-x) to boost the electrochemical NRR performance. The induced effects of C dopants and S vacancies of Sb2S3 on the physical and electrochemical behaviors were throughly investigated. Experiments verify that, the content of low oxidation state in Sb species are remarkably enhanced after introducing C dopants and S vacancies, this facilitate the enhanced electric conductivity and NRR activities of C-Sb2S3-x, together with the encouraged reaction kinetics. The prepared C-Sb2S3-x delivered an optimized NH3 yield rate of 47.2 μg h−1 mg−1cat. at −0.6 V along with a high Faradaic efficiency value of 6.4 % at −0.5 V in acid, outperforming than those of Sb2S3 and most disclosed sulfid NRR electrocatalysts. Density functional theory calculations validate that, cooperation of C doping and S vacancy could achieve the elevated NH3 yield rate, Faradaic efficiency as well as competitive stability. This approach puts forward an effective strategy for transition metal compounds to be more suitable for efficient electrocatalysis.

Enhanced N2 Adsorption and Activation by Combining Re Clusters and In Vacancies as Dual Sites for Efficient and Selective Electrochemical NH3 Synthesis.

The electrochemical N2 reduction reaction (NRR) is a green and energy-saving sustainable technology for NH3 production. However, high activity and high selectivity can hardly be achieved in the same catalyst, which severely restricts the development of the electrochemical NRR. In2Se3 with partially occupied p-orbitals can suppress the H2 evolution reaction (HER), which shows excellent selectivity in the electrochemical NRR. The presence of VIn can simultaneously provide active sites and confine Re clusters through strong charge transfer. Additionally, well-isolated Re clusters stabilized on In2Se3 by the confinement effect of VIn result in Re-VIn active sites with maximum availability. By combining Re clusters and VIn as dual sites for spontaneous N2 adsorption and activation, the electrochemical NRR performance is enhanced significantly. As a result, the Re-In2Se3-VIn/CC catalyst delivers a high NH3 yield rate (26.63 μg h-1 cm-2) and high FEs (30.8%) at -0.5 V vs RHE.

Computational screening of pyrazine-based graphene-supported transition metals as single-atom catalysts for the nitrogen reduction reaction.

Electrochemical synthesis of NH3 from N2 utilizing single-atom catalysts (SACs) is a promising strategy for industrial nitrogen fixation and chemical raw material production. In this work, single transition metals (TMs) anchored on pyrazine-based graphene (TM@py-GY) are systematically studied to screen potential electrocatalysts for the nitrogen reduction reaction (NRR) using first-principles calculations. Particularly, the descriptor φ related to electronegativity and valence electron number is selected to clarify the trend of NRR activity, realizing a fast-scan/estimation among various candidates. After a four-step screening process, WI@py-GY and MoII@py-GY SACs are screened with good structural stability, high selectivity, and high activity. Meanwhile, the thermodynamic stability of WI@py-GY and MoII@py-GY SACs is demonstrated to ensure their feasibility in real experimental conditions. Furthermore, electronic properties are also examined in detail to analyze activity origin. This work not only provides an effective and reliable method for screening electrochemical NRR catalysts with excellent performance but also provides guidance for the rational design of SACs.

*H migration-assisted MvK mechanism for efficient electrochemical NH3 synthesis over TM-TiNO.

The electrochemical NH3 synthesis on TiNO is proposed to follow the Mars-van Krevelen (MvK) mechanism, offering more favorable N2 adsorption and activation on the N vacancy (Nv) site, compared to the conventional associative mechanism. The regeneration cycle of Nv represents the rate-determining step in this process. This study investigates a series of TM (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt)-TiNO to explore the *H migration (from TM to TiNO)-promoted Nv cycle. The screening results indicate that Ni-TiNO exhibits strong H2O decomposition for *H production with 0.242 eV and low *H migration resistance with 0.913 eV. Notably, *H migration from Ni to TiNO significantly reduces the Nv formation energy to 0.811 eV, compared to 1.387 eV on pure TiNO. Meanwhile, in the presence of *H, Nv formation takes precedence over Tiv and Ov. Lastly, electronic performance calculations reveal that the collaborative function provided by Ni and Nv enables highly stable and efficient NH3 synthesis. The *H migration-assisted MvK mechanism demonstrates effective catalytic cycle performance in electrochemical N2 fixation and may have potential applicability to other hydrogenation reactions utilizing water as a proton source.

Tungsten Nitride/Tungsten Oxide Nanosheets for Enhanced Oxynitride Intermediate Adsorption and Hydrogenation in Nitrate Electroreduction to Ammonia.

Electrochemical NO3- reduction reaction (NO3RR) is a promising technique for green NH3 synthesis. Tungsten oxide (WO3) has been regarded as an effective electrocatalyst for electrochemical NH3 synthesis. However, the weak adsorption and the sluggish hydrogenation of oxynitride intermediates (NOx, e.g., *NO3 and *NO2) over WO3 materials hinder the efficiency of converting NO3- to NH3. Herein, we design a heterostructure of tungsten nitride (WN) and WO3 (WN/WO3) nanosheets to optimize *NO3 and *NO2 adsorptions and facilitate *NO2 hydrogenations to achieve a highly efficient electrochemical NO3RR to produce NH3. Theoretical calculations predict that locally introducing WN into WO3 will shorten the distance between adjacent W atoms, resulting in *NO3 and *NO2 being strongly adsorbed on W active sites in the form of bidentate ligands instead of the relatively weak monodentate ligands. Furthermore, WN facilitates H2O dissociation to supply the requisite protons, which is beneficial for *NO2 hydrogenations. Inspired by theoretical prediction, WN/WO3 nanosheets are successfully fabricated through a high-temperature nitridation process. The transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption near-edge spectroscopy investigations confirm that the amorphous WN has been locally introduced in situ into WO3 nanosheets to form a composite heterostructure. The as-prepared WN/WO3 nanosheets exhibit a high Faraday efficiency of 88.9 ± 7.2% and an appreciable yield rate of 8.4 mg h-1 cm-2 toward NH3 production, which is much higher than that of individual WO3 and WN. The enhanced adsorption and hydrogenation behaviors of *NOx over WN/WO3 are characterized by in situ Fourier-transform infrared spectroscopy, consistent with the theoretical predictions. This work develops facile and effective heterostructure nanomaterials to tune the adsorption and hydrogenation of NOx for boosting the efficiency from NO3- to NH3.

Simultaneously Enhancing Adsorbed Hydrogen and Dinitrogen to Enable Efficient Electrochemical NH3 Synthesis on Sm(OH)3

The electrochemical N2 reduction reaction (ENRR), driven by renewable electricity and run under ambient conditions, offers a promising sustainable avenue for carbon‐neutral NH3 production. Yet, to efficiently bind and activate the inert N2 remains challenge. Herein, effective and stable electrochemical NH3 synthesis on Sm(OH)3 via enhanced adsorption of hydrogen and dinitrogen by dual integration of sulfur dopants and oxygen vacancies (VO) is reported. The resulting S‐doped lanthanide electrocatalyst attains both a good NH3 yield rate, exceeding 21 μgNH3 h−1 mgcat.−1, and an NH3 faradaic efficiency of over 29% at −0.3 V (vs reversible hydrogen electrode) in an H‐type cell using a neutral electrolyte, figures of merit that are largely maintained after 2 days of consecutive polarization. Density functional theory calculations show that the adsorption energy barrier of N2 on S‐Sm(OH)3(VO) is greatly lowered by the introduction of VO. In addition, the S sites improve the adsorption of hydrogen produced via the Volmer reaction, which is conducive to the formation of the *N–NH intermediate (i.e., the potential determining step, PDS) on adjacent Sm sites, and thereby significantly promotes the reaction kinetics of ENRR. The PDS free energy for the catalyst is comparable with the values at the peak of the ENRR volcano plots of leading transition metal catalyst surfaces.

A first-principles study of transition metal clusters supported on graphene as electrocatalysts for N2 to NH3 reaction

NH3 is an important raw material for a variety of chemicals, but also an important carbon-free energy carrier. Currently, NH3 synthesis mainly relies on Habor–Bosch method with high energy consumption, high pollution and low efficiency. So it is urgent to develop a green process for NH3 synthesis. The electrochemical NH3 synthesis can be carried out under ambient conditions. Therefore, it is very important to find electrocatalysts with good stability, high activity and excellent selectivity. Here, we have designed homonuclear transition metal (TM = Fe, Co, Ni) clusters catalyst supported on graphene (TM3 @Gra) as electrocatalysts for nitrogen reduction reaction (NRR). The mechanism of electrocatalytic NRR on TM3 @Gra was investigated. The Fe3 @Gra, Co3 @Gra, and Ni3 @Gra showed high catalytic activity with corresponding limiting potential of –0.60, –0.64 and −0.45 V, respectively. Finally, the selectivity and thermal stability analysis confirmed that TM3 @Gra were the ideal NRR electrocatalysts. We hope that the results of this study will facilitate the design and development of NRR catalysts and provide theoretical reference for the rational design of cluster catalysts.

Dinitrogen Reduction Coupled with Methanol Oxidation for Low Overpotential Electrochemical NH3 Synthesis Over Cobalt Pyrophosphate as Bifunctional Catalyst.

Electrochemical dinitrogen (N2 ) reduction to ammonia (NH3 ) coupled with methanol electro-oxidation is presented in the current work. Here, methanol oxidation reaction (MOR) is proposed as an alternative anode reaction to oxygen evolution reaction (OER) to accomplish electrons-induced reduction of N2 to NH3 at cathode and oxidation of methanol at anode in alkaline media thereby reducing the overall cell voltage for ammonia production. Cobalt pyrophosphate micro-flowers assembled by nanosheets are synthesized via a surfactant-assisted sonochemical approach. By virtue of structural and morphological advantages, the maximum Faradaic efficiency of 43.37% and NH3 yield rate of 159.6µg h-1 mgca -1 is achieved at a potential of -0.2V versus RHE. The proposed catalyst is shown to also exhibit a very high activity (100mA mg-1 at 1.48V), durability (2h) and production of value-added formic acid at anode (2.78µmol h-1 mgcat -1 and F.E. of 59.2%). The overall NH3 synthesis is achieved at a reduced cell voltage of 1.6V (200mV less than NRR-OER coupled NH3 synthesis) when OER at anode is replaced with MOR and a high NH3 yield rate of 95.2µg h-1 mgcat -1 and HCOOH formation rate of 2.53µmol h-1 mg-1 are witnessed under full-cell conditions.

Efficient Ammonia Synthesis from Nitrate Catalyzed by Au/Cu with Enhanced Adsorption Ability

The traditional method for synthesizing NH3 is the Haber–Bosch process which results in high‐fuel consumption and environmental pollution. Therefore, ecofriendly electrochemical synthesis of NH3 through nitrate (NO3−) reduction is a good choice. Herein, an integral Au/Cu electrode to catalyze NO3− reduction to NH3 is introduced. The catalyst exhibits not only the highest NH3 yield rate (73.4 mg h−1 cm−2) up to now but also a very high Faradaic efficiency of 98.02% at −0.7 V at room temperature. It is commonly believed that the transformation of NO3− to nitrite (NO2−) is an obstacle to the NH3 generation from NO3− reduction. Surprisingly, unlike most of the other catalysts, Au/Cu exhibits better activity for NO3− reduction than that for NO2− reduction. Based on the detailed experimental and density functional theory calculations, the excellent performance of Au/Cu for selective NO3− reduction lies in the enhanced adsorption capabilities of Au/Cu to NO3− in the alkaline environment and the lower energy barriers of the electrochemical reduction reaction.

Computational screening of single-atom catalysts for direct electrochemical NH3 synthesis from NO on defective boron phosphide monolayer

Selective electrocatalytic reduction of NO to ammonia provides a promising way to remove pollutant NO and realize green ammonia synthesis under ambient conditions. The key to promote the practical application of NO reduction reaction (NORR) is to develop economical and efficient electrocatalysts to replace Pt-based catalysts. In this work, we designed a series of transition metal (TM) single-atom catalysts (SACs) supported on BP monolayer with a B vacancy (TM@BP, TM = Ti ∼ Zn, Zr ∼ Ag, and Hf ∼ Au), and systematically investigated their performance of electrocatalytic NORR by means of density functional theory (DFT). Taking the changes of free energy of the first (NO → NOH/NO → NHO) and last (OH → H2O/NH2 → NH3) hydrogenation steps of NORR as the screening criteria, seven TM@BP (TM = Ti, V, Cu, Rh, Ag, Ir, and Au) were selected from eighteen candidates. All possible reaction pathways of NORR to produce NH3 and byproducts (N2O, N2 and H2) were considered. Our calculated results show that Ti@BP, V@BP, Cu@BP, and Au@BP not only exhibit similar catalytic activity to Pt-based catalysts, but also have excellent NORR selectivity toward NH3, so they are predicted to be the most promising catalysts. This work provides useful guidance for the design and exploration of efficient NORR electrocatalysts.

Nanoreactor Based on Cyclodextrin for Direct Electrocatalyzed Ammonia Synthesis.

The high-efficiency transition metal-free electrocatalytic nitrate reduction reaction (NO3-RR) for ammonia synthesis has received more attention because of its green and environmentally friendly characteristics. Here, we report an efficient electrochemical NH3 synthesis directly from purely organic macrocyclic compounds α-, β-, and γ-cyclodextrins (CDs)-catalyzed transition metal-free electroreduction of nitrate under ambient conditions. In comparison with α-, and β-CDs, parent γ-CD presented uncommon catalytic performance with a relatively higher NH3 yield that can reach up to 2.28 mg h-1 cm-2 with a Faradaic efficiency (FE) of 63.2% at -0.9 V versus a reversible hydrogen electrode in alkaline medium, and the potassium ion-coordinated γ-CD complex can achieve a maximum NH3 production rate up to 4.66 mg h-1 cm-2 with an NH3 FE of 79.3%. Further comparison with permethyl-γ-CD, d-glucose, and poly(vinyl alcohol) for the NO3-RR indicated that the typical torus-shaped cyclic conformation and edge hydroxyl groups of parent CDs play important roles in the electrocatalytic process. The K+-mediated 3D γ-CD-K+ frameworks containing six CDs as nanoreactors greatly strengthen the enrichment effect of nitrate through hydrogen-bonding interaction and electrostatic interaction and promote the mass transfer, thus leading to the efficient NO3-RR in an alkaline electrolyte. This work provides a convenient, green, and economic method for high-performance NO3-RR, which has potential applications in the fields of environment, energy, and industry.

Recent progress in electrochemical synthesis of carbon-free hydrogen carrier ammonia and ammonia fuel cells: A review

Ammonia (NH3) is a cornerstone widely used in the modern agriculture and industry, the annual global production gradually increases to almost 200 million tons. Nearly 80% of the produced NH3 is used in the fertilizer industry and is essential for the development of global agriculture and consequently for maintaining population growth. Furthermore, NH3 can power hydrogen (H2) fueled devices, such as H2 fuel cells (FC), to use the interconversion between chemical energy and electric energy of nitrogen (N2) cycle, which can effectively alleviate the intermittent problems of renewable energy. However, the problems faced by NH3 in storage and release still restrict its development. Herein, this review introduces the latest research and development of electrochemical NH3 synthesis and direct NH3 FC, as well as outlines the technical challenges, possible improvement measures and development perspectives. N2 reduction reaction (NRR) and nitrate reduction reaction (NO3−RR) are two potential approaches for electrochemical NH3 synthesis. However, the existing research foundation still faces challenges in achieving high selectivity and efficiency. Direct NH3 FC are easy to transport and are expected to be widely used in mobile energy consuming equipment, but also limited by the lack of highly active and stable NH3 oxidation electrocatalysts. The perspectives of ammonia fuel cells as an alternative green energy are discussed.

Favorable Role of the Metal-Support Perimeter Region in Electrochemical NH3 Synthesis: A Density Functional Theory Study on Ru/BaCeO3.

The catalytic electrochemical synthesis of NH3 on Ru/BaCeO3 was investigated using density functional theory. The competition between NH3 formation and the hydrogen evolution reaction (HER) is a key for a high NH3 formation rate. Our calculations show that H adsorbs more strongly than N2 at the Ru particle moiety, while the adsorption of N2 is stronger than the H adsorption at the Ru/BaCeO3 perimeter, a model for the triple-phase boundary that is proposed to be an active site by experimental studies. This indicates that, while the HER is more favorable at the Ru particle moiety, it should be suppressed at the Ru/BaCeO3 perimeter. We also calculated the Gibbs free energy changes along the NH3 formation and found that the N2H formation, the NHNH2 formation, and the NH3 formation steps have a relatively large Gibbs energy change. Therefore, these are possible candidates for the potential-determining step. The calculated equilibrium potential (U = −0.70 V, vs RHE) is in reasonable agreement with experiments. We also evaluated the reaction energy (ΔE) and the activation barrier (Ea) of the N2H formation at several sites. ΔE and Ea were high at the Ru particle moiety (ΔE = 1.18 eV and Ea = 1.38 eV) but became low (ΔE = 0.32 eV and Ea = 1.31 eV) at the Ru/BaCeO3 perimeter. These provide the atomic-scale mechanism how the proton conduction in BaCeO3 assists the electrochemical NH3 synthesis.

Bismuth Ferrite as an Electrocatalyst for the Electrochemical Nitrate Reduction.

Electrochemical nitrate reduction has become an appealing "waste-to-wealth" approach for sustainable NH3 synthesis owing to its mild operating conditions. However, developing catalysts with high activities and Faradaic efficiencies for this complicated eight-electron reaction is a great challenge. Herein, bismuth ferrite (BiFeO3) flakes, with a distorted perovskite-type structure, are demonstrated to be excellent catalysts for electrochemical NH3 synthesis via nitrate reduction, with a maximum Faradaic efficiency of 96.85%, NH3 yield of 90.45 mg h-1 mgcat-1, at -0.6 V vs. reversible hydrogen electrode. During the nitrate reduction reaction, the crystalline BiFeO3 rapidly converts into an amorphous phase, which is stable in the long term reaction. These results open a new window for rational design of more active and durable electrocatalysts.

Heterogeneous Pd-PdO mesoporous film for ammonia electrosynthesis

Exploring cost-effective and highly active electrocatalysts is of great significance for sustainable electrochemical NH3 synthesis. Palladium (Pd)-based catalysts have been unanimously considered as one of the most efficient catalysts for the nitrogen reduction reaction (NRR). Herein, self-supported mesoporous Pd film with partial oxidation on Ni foam (mPd-PdO/NF) was synthesized through the micelle-assisted chemical replacement method coupled with air oxidation under 260 °C, and the mPd-PdO/NF electrocatalyst exhibited superior NRR performance with the maximum values of r NH3 (24.8 mg h−1 mgcat. −1) and FE (16.64%) were obtained at −0.1 V, relative to the single counterparts (mPd/NF and mPdO/NF). It is proposed that both metallic Pd and its oxide domains when co-existing with a phase boundary between them can facilitate nitrogen activation and hydrogenation, resulting in an enhanced NRR performance. This work provides an inspiring strategy for the rational design of highly active and durable metal–metal–oxide nanoarchitectonics for ammonia electrosynthesis.

Ambient Electrochemical Nitrogen Fixation over a Bifunctional Mo–(O–C2)4 Site Catalyst

The electrochemical synthesis of NH3 and NO3– by the N2 reduction reaction (NRR) and the N2 oxidation reaction (NOR) under ambient conditions utilizing H2O as the hydrogen and oxygen source has aroused great attention. Here, we report the fabrication of oxygen-coordinated molybdenum (Mo) single atoms anchored on carbon (Mo–O–C) using bacterial cellulose (BC) as the impregnation regulator and carbon source. As a result, the as-synthesized Mo–O–C as an electrocatalyst exhibits superior bifunctional NRR and NOR activities with high stability. A superb NH3 yield rate of 248.6 ± 12.9 μg h–1 mgcat.–1 and a faradaic efficiency (FE) of 43.8 ± 2.3% can be obtained at −0.20 V (vs RHE) by the Mo–O–C-catalyzed NRR, and Mo–O–C can also afford a NO3– yield rate of 217.1 ± 13.5 μg h–1 mgcat.–1 with a FE of 7.8 ± 0.5% at 2.35 V (vs RHE) for the NOR. The synchrotron-based X-ray absorption spectra and theoretical calculation results unveil that the O-coordinated molybdenum configuration of Mo–(O–C2)4 anchored on carbon is the most stable single-atom structure as the catalytic active sites for N2 adsorption, activation, and bifunctional hydrogenation/oxidation reactions.

High-Throughput Screening of Single-Atom Catalysts for Direct Electrochemical Nh3 Synthesis from No on Defective Boron Phosphide Monolayer

High-Throughput Screening of Single-Atom Catalysts for Direct Electrochemical Nh3 Synthesis from No on Defective Boron Phosphide Monolayer

Theoretical Study on V Atom Supported on N and P-Doped Defective Graphene for Electrocatalytic Nitrogen Reduction

Ammonia (NH3) is one of the most extensively produced chemicals worldwide, and it plays an important and indispensable role in the global economy. At present NH3 is mainly produced by the traditional Haber-Bosch process operated at high pressure and temperature, which results in massive energy consumption and carbon dioxide emissions. The electrochemical nitrogen reduction reaction (NRR) can allow the production of NH3 from nitrogen and water under ambient conditions and is regarded as a sustainable alternative to the Haber–Bosch process because of its low energy consumption and limited environmental impact. In this study, using density functional theory calculations, we designed a monovacancy defective graphene (MVG) doped with various nitrogen and phosphorus atoms and a single vanadium atom (VN1–3@MVG and VP1–3@MVG) to be used as electrocatalysts. The results revealed that N- and P-doping are beneficial for N2 adsorption and activation and can effectively reduce the energy barrier of the NRR, especially for P-doping. Among the synthesized electrocatalysts, double P-doped V@MVG demonstrated the best catalytic activity with a low free energy barrier of 0.43 eV. This paper reports the development of an efficient catalyst for electrochemical NH3 synthesis and provides valuable insights on the design of electrocatalysts with high activity and stability.