Strategic design of VO2 encased in N-doped carbon as an efficient electrocatalyst for the nitrogen reduction reaction in neutral and acidic media.

Electrocatalytic nitrogen fixation to ammonia (NH3), a precursor for fertilizer production and a promising energy carrier, has garnered widespread interest as an environment-friendly and sustainable alternative to the energy-intensive fossil-feedstock-dependent Haber-Bosch process. The large-scale deployment of this process is contingent on the identification of inexpensive, Earth-abundant systems that can operate efficiently, irrespective of the electrolyte pH for the selective production of NH3. In this regard, we discuss the scalable synthesis of VO2 anchored on N-doped carbon (VO2@CN), and its applicability as a robust electrocatalyst for the nitrogen reduction reaction (NRR). Benefitting from the presence of exposed VO2, which presumably acts as the active site for nitrogen reduction, and its activity over a broad pH range (from acidic to neutral), VO2@CN exhibits a high NH3 yield of 0.31 and 0.52 µmol h-1 mgcat-1 and a maximum Faradaic efficiency (FE) of 67.9% and 61.9% at -0.1 V vs. RHE, under neutral and acidic conditions, respectively. The obscured reaction intermediates of the NRR were identified from in situ ATR-IR studies under both electrolyte conditions. Additionally, the high selectivity of the catalyst was ascertained from the absence of hydrazine production and the competing hydrogen evolution reaction (HER). However, ammonia production underwent a reduction over 12 h of continuous operation presumably owing to the leaching of catalyst under these electrolysis conditions, which was more pronounced in electrolytes with acidic pH. Overall, the present report unveils the performance of an earth-abundant vanadium oxide-based system as an efficient electrocatalyst for the NRR under acidic and neutral pH conditions.

Deciphering the bridge oxygen vacancy-induced cascading charge effect for electrochemical ammonia synthesis.

Oxygen vacancy engineering has recently been gaining much interest as the charging effect it induces in a material can be used for varied applications. Usually, semiconductor materials act poorly in electrocatalysis, particularly in the nitrogen reduction reaction (NRR), owing to their inherent charge deficit and huge band gap. Vacancy introduction can be a viable material engineering route to make use of these materials for the NRR. However, a detailed investigation of the vacancy-type and its role for the structural reorientation and charge redistribution of a material is lagging in the field of NRRs. This work thus focuses on the synthesis of oxygen vacancy-engineered SnO2 with a gradual structural transformation from in-plane (iov) to bridge-type oxygen vacancy (bov) density. Consequently, the electron occupancy of the sp3d hybrid orbital changes, leading to an upshifted valence band maxima towards the Fermi level. This has a profound effect on the nature of N2 adsorption and the extent of NN bond polarization. Sn atoms adjacent to the bov are found to have a fair density of dangling charges that accomplish the NRR process at a comparatively low overpotential and determine the binding strength of the intermediates on the active site. The obscured yet stable reaction intermediates are thereby identified with in situ ATR-IR studies. A restricted hydrogen evolution reaction Faradaic on the Sn-site (favored over O-atoms) results in a Faradaic efficiency of 48.5%, which is better than that reported in all the literature reports on SnO2 for the NRR. This study thus unveils sufficient insights into the role of oxygen vacancies in a crystal as well as electronic structural alteration of SnO2 and the effect of active sites on the rate kinetics of the NRR.

Lewis Acid Mediated Alteration of Electron Density on a Copper Site via pπ-dπ Mixing Enhances the Electrochemical Nitrogen Reduction Reaction.

Strategic modulation of the electronic structure of the catalyst to foster the electrochemical nitrogen reduction reaction (eNRR) to the ammonia process significantly is still an area that needs to be explored. Herein, we report the incorporation of the Lewis acid into an electron-rich copper site regulating the electron density of the metal, which has been experimentally proved from the d-band center position to have a direct influence on the adsorption of N2 compared to the protons. The catalyst boron doped copper-cuprous oxide hybrid system (B-Cu/Cu2O) has shown promising Faradaic efficiency of 32% at -0.2 V vs reversible hydrogen electrode (RHE) compared to the pristine cuprous oxide (Cu2O(N)) system. The in situ Fourier transform infrared study confirms the presence of intermediates evolved during the electroreduction process. This study demonstrates the design of the active center with a specific push-pull interaction via the pπ-dπ bonding-antibonding approach and can shed light on the electrochemical activation and reduction of dinitrogen to produce ammonia.

Pd "Kills Two Birds with One Stone" for the Synthesis of Catalyst: Dual Active Sites of Pd Triggers the Kinetics of O2 Electrocatalysis.

Noble metal-based catalyst, despite their exorbitant cost, are the only successful catalyst for bifunctional oxygen electrocatalysis owing to their capability to drive forward the reaction rate kinetically. Therefore, it is desirable to diminish the noble metal loading without any compromise in the catalyst performance. In this study, the aim to achieve two goals with one action via a single-step route to have ultra-low loading of Pd in the catalyst. The Pd is used as a catalyst for C─C bond formation followed by complexation reactions or vice versa, in conventional Suzuki-Miyaura cross-coupling (SMCC) reaction, which yields a Pd-based porous organic polymer. Interestingly, it is found that dispersed Pd nanocluster (PdNC ) is present together with Pd single atom doped into nanocarbon (Pd-NC) matrix in the catalyst (PdNC /Pd-NC800 ) that obtained after pyrolysis of the porous polymer. The catalyst exhibits remarkable bifunctional activity and durability towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Further, it is studied that the in situ attenuated total reflection infrared (ATR-IR) spectroscopy at different electrochemical potentials during ORR and OER to observe the reaction intermediates. The homemade zinc-air battery with the catalyst displayed great performance, establishing the significance of PdNC /Pd-NC800 as a bifunctional oxygen electrocatalyst.

Laser-irradiated carbonized polyaniline-N-doped graphene heterostructure improves the cyclability of on-chip microsupercapacitor.

Laser-irradiated graphene-based heterostructures have attracted significant attention for the fabrication of highly conducting and stable metal-free energy storage devices. Heteroatom doping on the graphene backbone has proven to have better charge storage properties. Among other heteroatoms, nitrogen-doped graphene (NG) has been extensively researched due to its several advanced properties while maintaining the original characteristics of graphene for energy storage applications. However, NG is generally prepared via chemical vapor deposition or high temperature pyrolysis method, which gives low yield and has a complex operation route. In this work, first a polyaniline-reduce graphene oxide (PANI-rGO) heterostructure was prepared via in situ electrochemical polymerization, followed by the deposition process. In the next step, laser-irradiation process was employed to carbonize polyaniline as well as doping of nitrogen on the graphene film, simultaneously. For the very first time, laser-irradiated carbonization of PANI on NG (cPANI-NG) heterostructure was utilized for microsupercapacitor (MSC). The as-prepared cPANI-NG-MSC shows extremely high cycling stability with a capacitance enhancement of 135% of its initial capacitance after 70 000 continuous charge-discharge cycles. It is very interesting to know the origin of the capacitance enhancement, which results from the change of pyrrolic N in NG-MSC to the pyridinic and graphitic N. An on-chip NG-MSC exhibits an excellent charge storage capacitance of 43.5 mF cm-2 at a current density of 0.5 mA cm-2 and shows impressive power delivery at a very high scan rate of 100 V s-1. The excellent rate capability of the MSC shows capacitance retention up to 70.1% with the variation of current density. This unique approach to fabricate NG-MSC can have a broad range of applications as energy storage devices in the electronics market, as demonstrated by glowing a commercial red LED.

Engineering hydrophobic-aerophilic interfaces to boost N2 diffusion and reduction through functionalization of fluorine in second coordination spheres.

Ammonia is a crucial biochemical raw material for nitrogen containing fertilizers and a hydrogen energy carrier obtained from renewable energy sources. Electrocatalytic ammonia synthesis is a renewable and less-energy intensive way as compared to the conventional Haber-Bosch process. The electrochemical nitrogen reduction reaction (eNRR) is sluggish, primarily due to the deceleration by slow N2 diffusion, giving rise to competitive hydrogen evolution reaction (HER). Herein, we have engineered a catalyst to have hydrophobic and aerophilic nature via fluorinated copper phthalocyanine (F-CuPc) grafted with graphene to form a hybrid electrocatalyst, F-CuPc-G. The chemically functionalized fluorine moieties are present in the second coordination sphere, where it forms a three-phase interface. The hydrophobic layer of the catalyst fosters the diffusion of N2 molecules and the aerophilic characteristic helps N2 adsorption, which can effectively suppress the HER. The active metal center is present in the primary sphere available for the NRR with a viable amount of H+ to achieve a substantially high faradaic efficiency (FE) of 49.3% at -0.3 V vs. RHE. DFT calculations were performed to find out the rate determining step and to explore the full energy pathway. A DFT study indicates that the NRR process follows an alternating pathway, which was further supported by an in situ FTIR study by isolating the intermediates. This work provides insights into designing a catalyst with hydrophobic moieties in the second coordination sphere together with the aerophilic nature of the catalyst that helps to improve the overall FE of the NRR by eliminating the HER.

Ample Lewis Acidic Sites in Mg2B2O5 Facilitate N2 Electroreduction through Bonding-Antibonding Interactions.

Extensive research on the electrochemical nitrogen reduction reaction (NRR) has put forward a sound list of potential catalyst materials with properties inducing N2 adsorption, protonation, and reduction. However, rather than a random selection of catalysts, it is essential to understand the vitals in terms of orbital orientation and charge distribution that actually manipulate the rate-determining steps of NRR. Realizing these factors, herein we have explored a main group earth-abundant Mg-based electrocatalyst Mg2B2O5 for NRR due to the abundance of Lewis acid sites in the catalyst favoring the bonding-antibonding interactions with the N2 molecules. Positron annihilation studies indicate that the electronic charge distribution within the catalyst has shallow surface oxygen vacancies. These features in the catalyst enabled a sound Faradaic efficiency of 46.4% at -0.1 V vs reversible hydrogen electrode for the selective NH3 production in neutral electrolyte. In situ Fourier transform infrared suggests a maximum N-N bond polarization at -0.1 V and detected H-N-H and -NH2 intermediates during the course of the NRR on the catalyst surface. In a broader picture, the biocompatibility of Mg2+ diversifies the utility of this catalyst material in N2/biofuel cell applications that would certainly offer a green alternative toward our goal of a sustainable society.

Coordination Engineering of Dual Co, Ni Active Sites in N-Doped Carbon Fostering Reversible Oxygen Electrocatalysis.

The development of affordable and non-noble-metal-based reversible oxygen electrocatalysts is required for renewable energy conversion and storage systems like metal-air batteries (MABs). However, the nonbifunctionality of most of the catalysts impedes their use in rechargeable MAB applications. Moreover, the loss of active sites also affects the long-term performance of the electrocatalyst toward oxygen electrocatalysis. In this work, we report a simplistic yet controllable chemical approach for the synthesis of dual transitional metals such as cobalt, nickel, and nitrogen-doped carbon (CoNi-NC) as bifunctional electrode materials for rechargeable zinc-air batteries (ZABs). The spatially isolated Ni-N4 and Co-N4 active units were rendered for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively. The individual efficacy of both reversible reactions enables an ΔE value of ∼0.72 V, which outperforms several bifunctional electrocatalysts reported in the literature. The half-wave potential (E1/2) and overpotential were achieved at 0.83 V and 330 mV (vs RHE) for ORR and OER, respectively. The peak power density of ZAB equipped with the CoNi-NC catalyst was calculated to be 194 mW cm-2. The present strategy for the synthesis of bifunctional electrocatalysts with dual active sites offers prospects for developing electrochemical energy storage and conversion systems.

Elevating the energy efficiency for the power-to-ammonia conversion: Role of oxygen evolution reaction kinetics.

Electrochemical nitrogen reduction reaction (NRR) is imperatively countered with the oxygen evolution reaction (OER) on a conventional Pt counter electrode. Upon focusing on the development of suitable cathode catalysts, it is usually overseen that OER on Pt seeks a significant energy input to overcome the slow reaction kinetics, regardless of the efficiency of the NRR catalyst. Here, we unveil an out-of-the-box concept with state-of-the-art catalysts that, on pursuing OER with RuO2 in KOH, the NRR process reinforces thermodynamically. In this work, it has been shown how both the electrode and electrolyte simultaneously help to elevate a reaction mechanism in terms of Gibbs' energy and equilibrium constant. As a proof of concept, we assembled RuO2 with an NRR catalyst, iron phthalocyanine (FePc), in an electrolyzer, preferably in a two-electrode setup, where the catholyte consisted of 0.5M NaBF4. This system achieved selective cathodic conversion of N2 to NH3 with 67.6% Faradaic efficiency at 0.0 V (vs reversible hydrogen electrode) and simultaneous anodic water oxidation to O2 with a high electricity-to-chemical energy conversion efficiency of 46.7%. The electrolyzer forecasted a full cell voltage of 2.04 V, which demands only 603 mV overpotential to attain 0.5 mA current to drive forward the chemical equilibrium of the overall cell reaction. This study not only emphasized the importance of electrode-electrolyte improvisation but also provided a wider outlook in terms of different thermodynamic parameters to be considered to determine the efficiency of the overall NRR coupled OER process.

Engineering Catalytically Active Sites by Sculpting Artificial Edges on MoS2 Basal Plane for Dinitrogen Reduction at a Low Overpotential.

Engineering catalytically active sites have been a challenge so far and often relies on optimization of synthesis routes, which can at most provide quantitative enhancement of active facets, however, cannot provide control over choosing orientation, geometry and spatial distribution of the active sites. Artificially sculpting catalytically active sites via laser-etching technique can provide a new prospect in this field and offer a new species of nanocatalyst for achieving superior selectivity and attaining maximum yield via absolute control over defining their location and geometry of every active site at a nanoscale precision. In this work, a controlled protocol of artificial surface engineering is shown by focused laser irradiation on pristine MoS2 flakes, which are confirmed as catalytic sites by electrodeposition of AuNPs. The preferential Au deposited catalytic sites are found to be electrochemically active for nitrogen adsorption and its subsequent reduction due to the S-vacancies rather than Mo-vacancy, as advocated by DFT analysis. The catalytic performance of Au-NR/MoS2 shows a high yield rate of ammonia (11.43 × 10-8  mol s-1 cm-2 ) at a potential as low as -0.1 V versus RHE and a notable Faradaic efficiency of 13.79% during the electrochemical nitrogen reduction in 0.1 m HCl.

Refining the Spectroscopic Detection Technique: A Pivot in the Electrochemical Ammonia Synthesis.

Ammonia has been recognized as the future fuel because of its immense advantages over liquid hydrogen. The research trend nowadays is mostly inclined toward the electrochemical ammonia synthesis since it offers a sustainable method of green ammonia production. The indophenol blue method is one of the largely used colorimetric techniques to detect ammonia spectroscopically but lacks a proper experimental protocol. The unresolved speculations related to this method concerning stability of dye, sequence of mixing of reagents, importance of pH in the dye formation, or sensitivity of the method to interferants need vigorous experimental verification and a legitimate protocol has to be set up for a reliable and reproducible data. This work thus aims to unveil the artefacts of this method and explore the mechanisms involved such that it becomes easy for a newcomer as well as existing researchers in the field to understand the requirement of rigorous optimizations in this technique.

Oxygen Functionalization-Induced Charging Effect on Boron Active Sites for High-Yield Electrocatalytic NH3 Production.

Ammonia has been recognized as the future renewable energy fuel because of its wide-ranging applications in H2 storage and transportation sector. In order to avoid the environmentally hazardous Haber-Bosch process, recently, the third-generation ambient ammonia synthesis has drawn phenomenal attention and thus tremendous efforts are devoted to developing efficient electrocatalysts that would circumvent the bottlenecks of the electrochemical nitrogen reduction reaction (NRR) like competitive hydrogen evolution reaction, poor selectivity of N2 on catalyst surface. Herein, we report the synthesis of an oxygen-functionalized boron carbonitride matrix via a two-step pyrolysis technique. The conductive BNCO(1000) architecture, the compatibility of B-2pz orbital with the N-2pz orbital and the charging effect over B due to the C and O edge-atoms in a pentagon altogether facilitate N2 adsorption on the B edge-active sites. The optimum electrolyte acidity with 0.1 M HCl and the lowered anion crowding effect aid the protonation steps of NRR via an associative alternating pathway, which gives a sufficiently high yield of ammonia (211.5 µg h-1 mgcat-1) on the optimized BNCO(1000) catalyst with a Faradaic efficiency of 34.7% at - 0.1 V vs RHE. This work thus offers a cost-effective electrode material and provides a contemporary idea about reinforcing the charging effect over the secured active sites for NRR by selectively choosing the electrolyte anions and functionalizing the active edges of the BNCO(1000) catalyst.

Inter-Electronic Interaction between Ni and Mo in Electrodeposited Ni-Mo-P on 3D Copper Foam Enables Hydrogen Evolution Reaction at Low Overpotential.

Electrocatalytic hydrogen evolution reaction (HER) via water electrolysis has been considered the most effective and sustainable route to produce clean hydrogen. Designing and structure optimization are the two important parameters to develop an affordable, easy to fabricate, and stable non-noble metal electrocatalyst for the production of hydrogen as a clean, sustainable, and green fuel. Herein, we have synthesized Ni-Mo-P on copper foam (Cuf) via a facile single-step electrodeposition method, which can show stratospheric efficiency toward HER with a Tafel slope of 67 mV dec-1 and a very low overpotential of only 53 mV at a current density of 20 mA cm-2. Cuf acts as a conducting substrate support and the existence of the inter-electronic effect between Ni and Mo results in substantial catalytic activity toward hydrogen generation. In addition to this, the catalyst shows long time stability of around 97.5 h with almost negligible degradation under the applied overpotential for HER in alkaline media. This work features the significance of structure design and construction of non-noble metal catalysts via a simple method for efficient hydrogen generation.

Ultrafine Mix-Phase SnO-SnO2 Nanoparticles Anchored on Reduced Graphene Oxide Boost Reversible Li-Ion Storage Capacity beyond Theoretical Limit.

Tin-based materials with high specific capacity have been studied as high-performance anodes for Li-ion storage devices. Herein, a mix-phase structure of SnO-SnO2@rGO (rGO = reduced graphene oxide) was designed and prepared via a simple chemical method, which leads to the growth of tiny nanoparticles of a mixture of two different tin oxide phases on the crumbled graphene nanosheets. The three-dimensional structure of graphene forms the conductive framework. The as-prepared mix phase SnO-SnO2@rGO exhibits a large Brunauer-Emmett-Teller surface area of 255 m2 g-1 and an excellent ionic diffusion rate. When the resulting mix-phase material was examined for Li-ion battery anode application, the SnO-SnO2@rGO was noted to deliver an ultrahigh reversible capacity of 2604 mA h g-1 at a current density of 0.1 A g-1. It also exhibited superior rate capabilities and more than 82% retention of capacity after 150 charge-discharge cycles at 0.1 A g-1, lasting until 500 cycles at 1 A g-1 with very good retention of the initial capacity. Owing to the uniform defects on the rGO matrix, the formation of LiOH upon lithiation has been suggested to be the primary cause of this very high reversible capacity, which is beyond the theoretical limit. A Li-ion full cell was assembled using LiNi0.5Mn0.3Co0.2O2 (NMC-532) as a high-capacity cathodic counterpart, which showed a very high reversible capacity of 570 mA h g-1 (based on the anode weight) at an applied current density of 0.1 A g-1 with more than 50% retention of capacity after 100 cycles. This work offers a favorable design of electrode material, namely, mix-phase tin oxide-nanocarbon matrix, exhibiting adequate electrochemical performance for Li storage applications.

Tuning the Electronic Structure of Cobalt Selenide on Copper Foam by Introducing a Ni Buffer Layer for Highly Efficient Electrochemical Water Splitting.

The development of a cost-effective, remarkably competent, and durable bifunctional electrocatalyst is the foremost requirement of water splitting to generate H2 fuel as a renewable energy technology. Three-dimensional porous copper foam (Cuf) when electrochemically decorated with transition metal selenide results in a highly active electrocatalyst for adequate water electrolysis. In terms of water splitting, the role of cobalt selenide and Cuf has already proven to be remarkable. The introduction of a Ni buffer layer between Cuf and cobalt selenide (Cuf@Ni-CoSe2) acts as a valve to enhance the electron thrust from the substrate to the material surface with no compromise in the overall material conductivity, which not only increases the efficiency and activity but also improves the stability of the catalyst. The self-supported synthesized catalyst material showed an admirable activity toward the oxygen evolution reaction and hydrogen evolution reaction in alkaline media. The performance of the catalyst was found to be significantly better than that of the noble catalyst RuO2. The catalyst was very stable up to 93 h and attained a full cell voltage of only 1.52 V at a current density of 10 mA cm-2. Therefore, for large-scale hydrogen production, this as-synthesized catalyst hss the potential to replace conventional fossil fuel-based energy systems.

Lewis acid-dominated aqueous electrolyte acting as co-catalyst and overcoming N2 activation issues on catalyst surface.

The growing demands for ammonia in agriculture and transportation fuel stimulate researchers to develop sustainable electrochemical methods to synthesize ammonia ambiently, to get past the energy-intensive Haber-Bosch process. However, the conventionally used aqueous electrolytes limit N2 solubility, leading to insufficient reactant molecules in the vicinity of the catalyst during electrochemical nitrogen reduction reaction (NRR). This hampers the yield and production rate of ammonia, irrespective of how efficient the catalyst is. Herein, we introduce an aqueous electrolyte (NaBF4), which not only acts as an N2-carrier in the medium but also works as a full-fledged "co-catalyst" along with our active material MnN4 to deliver a high yield of NH3 (328.59 µg h-1 mgcat-1) at 0.0 V versus reversible hydrogen electrode. BF3-induced charge polarization shifts the metal d-band center of the MnN4 unit close to the Fermi level, inviting N2 adsorption facilely. The Lewis acidity of the free BF3 molecules further propagates their importance in polarizing the N≡N bond of the adsorbed N2 and its first protonation. This push-pull kind of electronic interaction has been confirmed from the change in d-band center values of the MnN4 site as well as charge density distribution over our active model units, which turned out to be effective enough to lower the energy barrier of the potential determining steps of NRR. Consequently, a high production rate of NH3 (2.45 × 10-9 mol s-1 cm-2) was achieved, approaching the industrial scale where the source of NH3 was thoroughly studied and confirmed to be chiefly from the electrochemical reduction of the purged N2 gas.

Strategic Modulation of Target-Specific Isolated Fe,Co Single-Atom Active Sites for Oxygen Electrocatalysis Impacting High Power Zn-Air Battery.

An effective modulation of the active sites in a bifunctional electrocatalyst is essentially desired, and it is a challenge to outperform the state-of-the-art catalysts toward oxygen electrocatalysis. Herein, we report the development of a bifunctional electrocatalyst having target-specific Fe-N4/C and Co-N4/C isolated active sites, exhibiting a symbiotic effect on overall oxygen electrocatalysis performances. The dualism of N-dopants and binary metals lower the d-band centers of both Fe and Co in the Fe,Co,N-C catalyst, improving the overpotential of the overall electrocatalytic processes (ΔEORR-OER = 0.74 ± 0.02 V vs RHE). Finally, the Fe,Co,N-C showed a high areal power density of 198.4 mW cm-2 and 158 mW cm-2 in the respective liquid and solid-state Zn-air batteries (ZABs), demonstrating suitable candidature of the active material as air cathode material in ZABs.

Dual active sites in a triazine-based covalent organic polymeric framework promoting oxygen reduction reaction.

A new significant feature of a triazine-based covalent organic polymer electrocatalyst is demonstrated. The metal-free electrocatalyst has dual-active sites, which enable it to entangle oxygen via a push-pull interaction that plays a crucial role in promoting the oxygen reduction reaction.

Electronic interplay: synergism of binary transition metals and role of M-N-S site towards oxygen electrocatalysis.

Towards rational catalyst development, a binary Fe-Co centre has been coordinated with S and N in a nanocarbon matrix. An electronic drift between Fe-Co and an extended +R effect from the S dopants towards the metals through the pz orbital of N are beneficial for oxygen electrocatalysis and a zinc-air battery.

Alteration of Electronic Band Structure via a Metal-Semiconductor Interfacial Effect Enables High Faradaic Efficiency for Electrochemical Nitrogen Fixation.

The interface engineering strategy has been an emerging field in terms of material improvisation that not only alters the electronic band structure of a material but also induces beneficial effects on electrochemical performances. Particularly, it is of immense importance for the environmentally benign electrochemical nitrogen reduction reaction (NRR), which is potentially impeded by the competing hydrogen evolution reaction (HER). The main problem lies in the attainment of the desired current density at a negotiable potential where the NRR would dominate over the HER, which in turn hampers the Faradaic efficiency for the NRR. To circumvent this issue, catalyst development becomes necessary, which would display a weak affinity for H-adsorption suppressing the HER at the catalyst surface. Herein, we have adopted the interfacial engineering strategy to synthesize our electrocatalyst NPG@SnS2, which not only suppressed the HER on the active site but yielded 49.3% F.E. for the NRR. Extensive experimental work and DFT calculations regarded that due to the charge redistribution, the Mott-Schottky effect, and the band bending of SnS2 across the contact layer at the interface of NPG, the d-band center for the surface Sn atoms in NPG@SnS2 lowered, which resulted in favored adsorption of N2 on the Sn active site. This phenomenon was driven even forward by the upshift of the Fermi level, and eventually, a decrease was seen in the work function of the heterostructure that increased the conductivity of the material as compared to pristine SnS2. This strategy thus provides a field to methodically suppress the HER in the realm of improving the Faradaic efficiency for the NRR.