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A dynamic-regulated Pd-Fe-N electrocatalyst was effectively constructed with electron-donating and back-donating effects, which serves as an efficient engineering strategy to optimize the electrocatalytic activity. The designed PdFe3/FeN features a comprehensive electrocatalytic performance toward the nitrogen reduction reaction (NRR, yield rate of 29.94 µg h-1 mgcat-1 and FE of 38.43% at -0.2 V vs RHE) and oxygen evolution reaction (OER, 308 mV at 100 mA cm-2). Combining in situ ATR-FTIR, XAS, and DFT results, the role of the interstitial-N-dopant-induced electron sponge effect has been significantly elucidated in strengthening the electrocatalytic NRR process. Specifically, the introduction of a N dopant, an electron acceptor, initiates the generation of robust Lewis-acidic Fe sites, facilitating free N2 capture and bonding. Simultaneously, after NH3 adsorption, the N dopant can back-donate electrons to Fe sites, strengthening the NH3 deportation through weakening the Lewis acidity of Fe centers. Besides, the electron-deficient Fe sites contribute to the reconstruction of FeOOH, the real active species during the OER, which accelerates the four-electron reaction kinetics. This research offers a perspective on electrocatalyst design, potentially facilitating the evolution of advanced material engineering for efficient electrocatalytic synthesis and energy storage.
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Electrochemical synthesis of ammonia is a green and sustainable way for nitrogen fixation, but the development of efficient electrocatalysts still faces challenges. The modulation of electronic structure through interface engineering and vacancy engineering is a new approach to enhance the performance of electrocatalysts. In this work, a phosphorus-doped core-shell heterojunction P-Sb2S3/MoS2 was designed and synthesized by combining antimony, which is inert to H+ adsorption, with molybdenum, which has good affinity and reducibility with nitrogen. The synthesis involved both interfacial engineering and vacancy engineering strategies.DFT calculations demonstrate that the formationofSb2S3/MoS2 heterojunction enhances the creation of a built-in electric field, thereby expediting electron flow.Additionally, phosphorus doping induced the formation of abundant sulfur vacancies, significantly enhancing nitrogen adsorption performance in this material.As a result, our designed structure exhibited excellent NRR performance with an ammonia production rate of 41.22 µg·h-1·mg-1cat and a Faraday efficiency of 15.70 %.The unique structural of this catalyst contribute to a more optimal balance between the rate of ammonia production and the Faraday efficiency. The successful preparation of the highly efficient P-Sb2S3/MoS2 heterojunctionsprovidesanew strategyfor catalyst design in electrocatalytic nitrogen reduction.
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Regulating the adsorption of an intermediate on an electrocatalyst by manipulating the electron spin state of the transition metal is of great significance for promoting the activation of inert nitrogen molecules (N2) during the electrocatalytic nitrogen reduction reaction (eNRR). However, achieving this remains challenging. Herein, a novel 2D/2D Mott-Schottky heterojunction, Co9S8/Nb2CTx-P, is developed as an eNRR catalyst. This is achieved through the in situ growth of cobalt sulfide (Co9S8) nanosheets over a Nb2CTx MXene using a solution plasma modification method. Transformation of the Co spin state from low (t2g 6eg 1) to high (t2g 5eg 2) is achieved by adjusting the interface electronic structure and sulfur vacancy of Co9S8/Nb2CTx-P. The adsorption ability of N2 is optimized through high spin Co(II) with more unpaired electrons, significantly accelerating the *N2â*NNH kinetic process. The Co9S8/Nb2CTx-P exhibits a high NH3 yield of 62.62 µg h-1 mgcat. -1 and a Faradaic efficiency (FE) of 30.33% at -0.40 V versus the reversible hydrogen electrode (RHE) in 0.1 m HCl. Additionally, it achieves an NH3 yield of 41.47 µg h-1 mgcat. -1 and FE of 23.19% at -0.60 V versus RHE in 0.1 m Na2SO4. This work demonstrates a promising strategy for constructing heterojunction electrocatalysts for efficient eNRR.
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Utilizing hot carriers for efficient plasmonic-mediated chemical reactions (PMCRs) to convert solar energy into secondary energy is one of the most feasible solutions to the global environmental and energy crisis. Finding a plasmonic heterogeneous nanostructure with a more efficient and reasonable hot carrier transport path without affecting the intrinsic plasmonic properties is still a major challenge that urgently needs to be solved in this field. Herein, the mechanism by which plasmonic-promoted interatomic hot electron redistribution on the surface of Au3Cu alloy nanoparticles promotes the electrocatalytic nitrogen reduction reaction (ENRR) is successfully clarified. The localized surface plasmon resonance (LSPR) effect can boost the transfer of plasmonic hot electrons from Au atoms to Cu atoms, trigger the interatomic electron regulation of Au3Cu alloy nanoparticles, enhance the desorption of ammonia molecules, and increase the ammonia yield by approximately 93.9%. This work provides an important reference for rationally designing and utilizing the LSPR effect to efficiently regulate the distribution and mechanism of plasmonic hot carriers on the surface of heterogeneous alloy nanostructures.
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The electrochemical reduction of nitrogen to produce ammonia is pivotal in modern society due to its environmental friendliness and the substantial influence that ammonia has on food, chemicals, and energy. However, the current electrochemical nitrogen reduction reaction (NRR) mechanism is still imperfect, which seriously impedes the development of NRR. In situ characterization techniques offer insight into the alterations taking place at the electrode/electrolyte interface throughout the NRR process, thereby helping us to explore the NRR mechanism in-depth and ultimately promote the development of efficient catalytic systems for NRR. Herein, we introduce the popular theories and mechanisms of the electrochemical NRR and provide an extensive overview on the application of various in situ characterization approaches for on-site detection of reaction intermediates and catalyst transformations during electrocatalytic NRR processes, including different optical techniques, X-ray-based techniques, electron microscopy, and scanning probe microscopy. Finally, some major challenges and future directions of these in situ techniques are proposed.
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Developing active sites with flexibility and diversity is crucial for single atom catalysts (SACs) towards sustainable nitrogen fixation at ambient conditions. Herein, the effects of doping main group metal elements (MGM) on the stability, catalytic activity, and selectivity of vanadium-based SACs is systematically investigated based on density functional theory calculations. It is found that the catalytic activity of V site can be significantly enhanced by the synergistic effect between MGM and vanadium atoms. More importantly, a volcano curve between the catalytic activity and the adsorption free energy of NNH* can be established, in which V-Pb dimer embedded on N-coordinated graphene (VPb-NG) exhibits optimal NRR activity due to its location at the top of volcano. Further analysis of electronic structures reveals that the unoccupancy ratio (eg/t2g) of V site is dramatically increased by the strong d-p orbital hybridization between V and Pb atoms, subsequently, N2 is activated to a larger extent. These interesting findings may provide a new path for designing active sites in SACs with excellent performance.
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The electrochemical nitrogen reduction reaction is a crucial process for the sustainable production of ammonia for energy and agriculture applications. However, the reaction's efficiency is highly dependent on the activation of the inert N≡N bond, which is hindered by the electron back-donation to the π* orbitals of the N≡N bond, resulting in low eNRR capacity. Herein, we report a main-group metal-non-metal (O-In-S) eNRR catalyst featuring a dynamic proton bridge, with In-S serving as the polarization pair and O functioning as the dynamic electron pool. In-situ spectroscopic analysis and theoretical calculations reveal that the In-S polarization pair acts as asymmetric dual-sites, polarizing the N≡N bond by concurrently back-donating electrons to both the πx* and πy* orbitals of N2, thereby overcoming the significant band gap limitations, while inhibiting the competitive hydrogen evolution reaction. Meanwhile, the O dynamic electron pool acts as a "repository" for electron storage and donation to the In-S polarization pair. As a result, the O-In-S dynamic proton bridge exhibits exceptional NH3 yield rates and Faradaic efficiencies (FEs) across a wide potential window of 0.3 V, with an optimal NH3 yield of 80.07 ± 4.25 µg h-1 mg-1 and an FE of 38.01 ± 2.02%, outperforming most previously reported catalysts.
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In the electrochemical nitrogen reduction reaction (NRR), a leverage relationship exists between NH3-producing activity and selectivity because of the competing hydrogen evolution reaction (HER), which means that high activity with strong protons adsorption causes low product selectivity. Herein, we design a novel metal-organic hydrogen bonding framework (MOHBF) material to modulate this leverage relationship by a hydrogen-bond-regulated proton transfer pathway. The MOHBF material was composited with reduced graphene oxide (rGO) to form a Ni-N2O2 molecular catalyst (Ni-N2O2/rGO). The unique structure of O atoms in Ni-O-C and N-O-H could form hydrogen bonds with H2O molecules to interfere with protons being directly adsorbed onto Ni active sites, thus regulating the proton transfer mechanism and slowing the HER kinetics, thereby modulating the leverage relationship. Moreover, this catalyst has abundant Ni-single-atom sites enriched with Ni-N/O coordination, conducive to the adsorption and activation of N2. The Ni-N2O2/rGO exhibits simultaneously enhanced activity and selectivity of NH3 production with a maximum NH3 yield rate of 209.7 µg h-1 mgcat.-1 and a Faradaic efficiency of 45.7%, outperforming other reported single-atom NRR catalysts.
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The development of sustainable and effective electrochemical nitrogen fixation catalysts is crucial for the mitigation of the terrible energy consumption resulting from the Haber-Bosch process. Molybdenum disulfide (MoS2) exhibits promise toward nitrogen reduction reaction (NRR) on account of its similar structure to natural nitrogenases MoFe-co but still undergoes serious challenges with unsatisfactory catalytic performance resulted from limited active sites, conductivity, and selectivity. In this work, Fe/Co/B codoped MoS2 ultrathin nanosheets are synthesized and verified as excellent NRR catalysts with high activity, selectivity, and durability. The FeCoB-MoS2 demonstrates a high ammonia yield of 36.99 µg h-1 mgcat-1 at -0.15 V vs RHE and Faraday efficiency (FE) of 30.65% at -0.10 V vs RHE in 0.1 M HCl. The experimental results and the density functional theory (DFT) calculations emphasize that codoping of Fe, Co, and B into MoS2 synergistically enhances its conductivity and optimizes the electronic structure of the catalyst, which significantly improves the electrocatalytic ammonia synthesis performance. This work broadens the potential and enlightens the strategy for designing efficient electrocatalysts in the NRR field.
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The electrocatalytic nitrogen reduction reaction (NRR) is a crucial process in addressing energy shortages and environmental concerns by synthesizing the NH3. However, the difficulty of N2 activation and fewer NRR active sites limit the application of NRR. Therefore, the NRR performance can be improved by rapid electron transport paths to participate in multi-electron reactions and N2 activation. Doping with transition metal element is a viable strategy to provide electrons and electronic channels in the NRR. This study focuses on the synthesis of Fe2(MoO4)3 (FeMo) and x%La-doped FeMo (x = 3, 5, 7, and 10) using the hydrothermal method. La-doping creates electron transport channels Fe2+-O2--Fe3+ and oxygen vacancies, achieving an equal molar ratio of Fe2+/Fe3+. This strategy enables the super-exchange in Fe2+-O2--Fe3+, and then enhances electron transport speed for a rapid hydrogenation reaction. Therefore, the synergistic effect of Fe2+/Fe3+ cycling and oxygen vacancies improves the NRR performance. Notably, 5%La-FeMo demonstrates the superior NRR performance (NH3 yield rate: 29.6 µg h-1 mgcat-1, Faradaic efficiency: 5.8%) at -0.8 V (vs. RHE). This work analyzes the influence of the catalyst electronic environment on the NRR performance based on the effect on different valence states of ions on electron transport.
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Development of an efficient electrocatalyst for the nitrogen reduction reaction (NRR) to serve as an sustainable alternative to the Haber-Bosch process has proven highly challenging. Single atom catalysts (SACs), which have the maximum atom utilization efficiency, are among the most promising candidates. Single atoms can be incorporated to a catalytic system by doping or substitution or by attaching a molecular coordination complex to a substrate and the different insertion modes allow the chemical environment to be varied. We have used DFT to investigate vanadium SACS for NRR activity with a focus on varying the coordination environment of the V atom. Phthalocyanine, porphyrin and graphene like coordination environments with varying N-coordination have been studied. Vanadium phthalocyanine (VphN4) is the most promising of the investigated systems. It features a high selectivity relative the HER reaction and relatively strong binding of N2 relatively H, which prevents poisoning of the surface by hydrogen. VphN4 also has the lowest overpotential among the studied systems. The electrocatalytic properties of VphN4 deposited as a monolayer on the Ag (111) surface have been investigated. This system, which already has been prepared, shows promising properties for use as a catalytic electrode for the NRR reaction.
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The urgent need to prepare clean energy by environmentally friendly and efficient methods, which has led to widespread attention on electrocatalytic nitrogen reduction reaction (NRR) for ammonia production. At present, single atom catalytic nitrogen reduction has become the earliest promising method for industrial production due to its high atomic utilization rate, high selectivity, high controllability, and high stability. However, how to quickly screen catalysts with high catalytic efficiency and selectivity in single-atom catalysts (SACs) remains a challenge. Herein, the 29 SACs are constructed from C6N2 nanosheets doped with transition metals (TM@C6N2), which are analyzed for stability, adsorption performance, NRR catalytic activity, electronic properties, and competitiveness using first-principles calculations. The results show that Mo@C6N2 and Re@C6N2 exhibit the most outstanding catalytic performances, with limiting potentials (UL) of -0.29 and -0.31 V, respectively, in the solvent model. Machine learning is used to derive descriptors from the intrinsic features to predict the free energy changes for the potential-determining step. The importance of features is calculated, with the first ionisation energy (IE1) being the most significant influencing factor. Based on the guidance of machine learning and considering that IE1 is related to the ability of metal atoms to donate electrons, a four-step screening strategy using the Integrated Crystal Orbital Hamilton Populations (ICOHP) to screen catalysts instead of the traditional five-step screening not only improves the screening efficiency but also obtains completely consistent screening results. This work presents a new approach to predicting the catalytic performance of SACs and provides new insights into the influence of intrinsic properties on catalytic activity.
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Regulating the electron structure and precise loading sites of metal-active sites within the highly conjugated and porous covalent-triazine frameworks (CTFs) is essential to promoting the nitrogen reduction reaction (NRR) performance for electrocatalytic ammonia (NH3) synthesis under ambient conditions. Herein, experimental method and density functional theory (DFT) calculations were conducted to deeply probe the effect on NRR of the modulation of modulating the electron structure and the loading site of gold nanoparticles (Au NPs) in a two-dimensional (2D) CTF. 2D CTF synthesized using melem and hexaketocyclohexane octahydrate as building blocks (denoted as M-HCO-CTF) served as a robust scaffold for loading Au NPs to form an M-HCO-CTF@AuNP hybrid. DFT results uncovered that well-defined Au sites with tunable local structure were the active site for driving the NRR, which can significantly suppress the conversion of H+ into *H adsorption and enhance the nitrogen (N2) adsorption/activation. The overlapped Au (3d) and *N2 (2p) orbitals lowered the free energy of the rate-determining step to form *NNH, thereby accelerating the NRR. The M-HCO-CTF@AuNPs electrocatalyst exhibited a large NH3 yield rate of 66.3 µg h-1 mg-1cat. and a high Faraday efficiency of 31.4 % at - 0.2 V versus reversible hydrogen electrode in 0.1 M HCl, superior to most reported CTF-based ones. This work can provide deep insights into the modulation of the electron structure of metal atoms within a porous organic framework for artificial NH3 synthesis through NRR.
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Developing highly efficient single-atom catalysts (SACs) for the nitrogen reduction reaction (NRR) to ammonia production has garnered significant attention in the scientific community. However, achieving high activity and selectivity remains challenging due to the lack of innate activity in most existing catalysts or insufficient active site density. This study delves into the potential of M2C12 materials (M = Cr, Ir, Mn, Mo, Os, Re, Rh, Ru, W, Fe, Cu, and Ti) with high transition metal coverage as SACs for NRR using first-principles calculations. Among these materials, Os2C12 exhibited superior catalytic activity for NRR, with a low overpotential of 0.39 V and an Os coverage of up to 72.53 wt%. To further boost its catalytic activity, a nonmetal (NM) atom doping (NM = B, N, O, and S) and C vacancy modification were explored in Os2C12. It is found that the introduction of O enables exceptional catalytic activity, selectivity, and stability, with an even lower overpotential of 0.07 V. Incorporating the O atom disrupted the charge balance of its coordinating C atoms, effectively increasing the positive charge density of the Os-d-orbit-related electronic structure. This promoted strong d-π* coupling between Os and N2H, enhancing N2H adsorption and facilitating NRR processes. This comprehensive study provides valuable insights into NRR catalyst design for sustainable ammonia production and offers a reference for exploring alternative materials in other catalytic reactions.
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The electrochemical nitrogen reduction reaction (NRR) is an attractive pathway for producing ammonia under ambient conditions. The development of efficient catalysts for nitrogen fixation in electrochemical NRRs has become increasingly important, but it remains challenging due to the need to address the issues of activity and selectivity. Herein, using density functional theory (DFT), we explore ten kinds of triple transition metal atoms (M3 = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) anchored on the C2N monolayer (M3-C2N) as NRR electrocatalysts. The negative binding energies of M3 clusters on C2N mean that the triple transition metal clusters can be stably anchored on the N6 cavity of the C2N structure. As the first step of the NRR, the adsorption configurations of N2 show that the N2 on M3-C2N catalysts can be stably adsorbed in a side-on mode, except for Zn3-C2N. Moreover, the extended N-N bond length and electronic structure indicate that the N2 molecule has been fully activated on the M3-C2N surface. The results of limiting potential screen out the four M3-C2N catalysts (Co3-C2N, Cr3-C2N, Fe3-C2N, and Ni3-C2N) that have a superior electrochemical NRR performance, and the corresponding values are -0.61 V, -0.67 V, -0.63 V, and -0.66 V, respectively, which are smaller than those on Ru(0001). In addition, the detailed NRR mechanism studied shows that the alternating and enzymatic mechanisms of association pathways on Co3-C2N, Cr3-C2N, Fe3-C2N, and Ni3-C2N are more energetically favorable. In the end, the catalytic selectivity for NRR on M3-C2N is investigated through the performance of a hydrogen evolution reaction (HER) on them. We find that Co3-C2N, Cr3-C2N, Fe3-C2N, and Ni3-C2N catalysts possess a high catalytic activity for NRR and exhibit a strong capability of suppressing the competitive HER. Our findings provide a new strategy for designing NRR catalysts with high catalytic activity and selectivity.
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Rationally designing photocatalysts is crucial for the solar-driven nitrogen reduction reaction (NRR) due to the stable N≡N triple bond. Metal-organic frameworks (MOFs) are considered promising candidates but suffer from insufficient active sites and inferior charge transport. Herein, it is demonstrated that incorporating 3d metal ions, such as zinc (Zn) or iron (Fe) ions, into Al-coordinated porphyrin MOFs (Al-PMOFs) enables the enhanced ammonia yield of 88.7 and 65.0 µg gcat -1 h-1, 2.5- and 1.8-fold increase compared to the pristine Al-PMOF (35.4 µg gcat -1 h-1), respectively. The origin of ammonia (NH3) is verified via isotopic labeling experiments. Incorporating Zn or Fe into Al-PMOF generates active sites in Al-PMOF, that is, Zn-N4 or Fe-N4 sites, which not only facilitates the adsorption and activation of N2 molecules but suppresses the charge recombination. Photophysical and theoretical studies further reveal the upshift of the lowest unoccupied molecular orbital (LUMO) level to a more energetic position upon inserting 3d metal ions (with a more significant shift in Zn than Fe). The promoted nitrogen activation, suppressed charge recombination, and more negative LUMO levels in Al-PMOF(3d metal) contribute to a higher photocatalytic activity than pristine Al-PMOF. This work provides a promising strategy for designing photocatalysts for efficient solar-to-chemical conversion.
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Single-site molecular electrocatalysts, especially those that perform catalytic conversion of N2 to NH3 under mild conditions, are highly desirable to derive fundamental structure-activity relations and as potential alternatives to the current energy-consuming Haber-Bosch ammonia production process. Combining theoretical calculations with experimental evidence, it has been shown that easily reducible cobalt porphyrins catalyze the six-electron, six-proton reduction of dinitrogen to NH3 at neutral pH and under ambient conditions. Two easily reducible N-fused cobalt porphyrins - CoNHF and CoNHF(Br)2 - reveal NRR activity with Faradic efficiencies between 6 - 7.5% with ammonia yield rates of 300 - 340 µmol g-1 h-1. Contrary to this, much harder-to-reduce N-fused porphyrins - CoNHF(Ph)2 and CoNHF(PE)2 - reveal no NRR activity. The present study highlights the significance of tuning the redox and structural properties of single-site NRR electrocatalysts for improved NRR activity under mild conditions.
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Electrocatalytic nitrogen reduction reaction (NRR) is considered to be a viable contender for the production of NH3. However, due to the sluggish adsorption and activation of the electrocatalyst toward inert N2 molecules, there is an urgent need for developing effective catalysts to facilitate the reaction. Inspired by natural nitrogenase, in which Mo atoms are the active centers, Mo-based electrocatalysts have received considerable attention, but further exploration is still necessary. Interface-engineered electrocatalysts can effectively optimize the absorption and activation of the catalytic active center for N2 and thus improve the electrocatalytic activity of NRR. However, the lack of studies for controllably constructing an optimal ratio of two phases at the interface hinders the development of NRR electrocatalysts. Herein, a series of Mo2C/MoO2 interface-engineered electrocatalysts with various Mo2C/MoO2 ratios were constructed by controlling the Y dosages. The controlled experimental results verified that the catalytic activity of NRR, the dosage of Y, and the ratio of Mo2C/MoO2 were strongly correlated. Density functional theory calculations show that the C-Mo-O coordination at the Mo2C/MoO2 interface can optimize the reaction path and reduce the energy barrier of the reaction intermediates, thereby enhancing the reaction kinetics of NRR.
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Li-N2 batteries are a promising platform for electrochemical energy storage, but their performance is limited by the low activity of the cathode catalysts. In this work, density functional theory was used to study the catalytic activity of the pristine M2C and oxygen-functionalized M2CO2 MXenes (M = Sc, Ti, and V) as cathodes for Li-N2 batteries. The calculated results suggest that the pristine M2C MXenes (M = Sc, Ti, and V) show high electrical conductivity due to the Fermi level crossing the metal 3d states. The stable adsorption of N2 occurs on M2C MXenes via a side-on model and strengthens gradually with decreasing metal atomic number. Furthermore, the kinetics of N2 dissociation can be significantly accelerated by the coadsorption of Li on M2C MXenes. However, adsorption and dissociation of N2 on the M2CO2 surfaces are too difficult to occur due to strong electrostatic repulsion. The Li-mediated nitrogen reduction reaction during discharge proceeds favorably via (N + N)* â (LiN + N)* â (LiN + LiN)* â (Li2N + LiN)* â (Li2N + Li2N)* â (Li3N + Li2N)* â (Li3N + Li3N)* to form two isolated Li3N* on M2C MXenes. The calculated charge-discharge overpotentials decrease in the order of Sc2C < Ti2C < V2C. Notably, the Sc2C MXene has great potential as a cathode catalyst for Li-N2 batteries because of its high electrical conductivity, strong N2 adsorption, favorable Li-mediated N2 dissociation, and ultralow discharging, charging, and total overpotentials (0.07, 0.06, and 0.13 V). This study offers a theoretical foundation for future research on Li-N2 batteries.
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Doping is considered a promising material engineering strategy in electrochemical nitrogen reduction reaction (NRR), provided the role of the active site is rightly identified. This work concerns the doping of group VIB metal in Ag3PO4 to enhance the active site density, accompanied by d-p orbital mixing at the active site/N2 interface. Doping induces compressive strain in the Ag3PO4 lattice and inherently accompanies vacancy generation, the latter is quantified with positron annihilation lifetime studies (PALS). This eventually alters the metal d-electronic states relative to Fermi level and manipulate the active sites for NRR resulting into side-on N2 adsorption at the interface. The charge density deployment reveals Mo as the most efficient dopant, attaining a minimum NRR overpotential, as confirmed by the detailed kinetic study with the rotating ring disk electrode (RRDE) technique. In fact, the Pt ring of RRDE fails to detect N2H4, which is formed as a stable intermediate on the electrode surface, as identified from in-situ attenuated total reflectance-infrared (ATR-IR) spectroscopy. This advocates the complete conversion of N2 to NH3 on Mo/Ag3PO4-10 and the so-formed oxygen vacancies formed during doping act as proton scavengers suppressing hydrogen evolution reaction resulting into a Faradaic efficiency of 54.8% for NRR.