Strong Catalyst-support Interaction Research Articles

Efficient Co0.85Se-CNT sulfur cathode derived from strong catalyst-support interactions: Contribution of adsorption-catalysis mechanism to the redox kinetics of polysulfides

The sluggish conversion chemistry and the notorious ‘shuttle effect’ of lithium polysulfides (LiPSs) are hindering the widespread application of lithium-sulfur batteries (LSBs). Herein, N-doped carbon nanotubes arrays anchored with highly dispersed Co0.85Se nanoparticles were in-situ grown on 3D carbon paper substrates (Co0.85Se-CNT@CP) to promote redox kinetic. The derived sulfur cathode (S/Co0.85Se-CNT@CP) exhibited a sufficient chemisorption ability to accelerate the conversion kinetics and showed considerable capability (1210 mAh/g at 0.2C) and impressive cyclic stability (516 mAh/g at 2.0C after 500cycles). Even at a high loading of 6.0 mg cm−2, the assembled batteries performed a high capacity of 500 mAh/g at 2.0C after 500cycles. The exceptional performance is attributed to the following reasons: On the one hand, the highly efficient conductive carbon nanotubes not only offer sufficient accommodation space for sulfur, but also provide physically confinement for polysulfides. On the other hand, the Co0.85Se nanoclusters drove the transformation of more elemental sulfur to Li2S2/Li2S. In addition, the S/Co0.85Se-CNT@CP did not require conventional binders, thus enhanced surface the reaction kinetic and electron transfer. The associated conversion mechanism was studied by ex-situ XPS, and an adsorption-catalytic model was established to elucidate the electrochemical mechanism. This study proposes a feasible strategy to solve the severe LiPSs shuttling and the sluggish conversion kinetics of LSBs.

High-entropy PtCuSnWNb nanoalloys as efficient and stable catalysts for ethanol oxidation electrocatalysis.

Ternary nanoalloys used as electrochemical ethanol oxidation catalysts for direct ethanol fuel cells are confronted with poor stability issues under harsh acidic operating conditions. To address this issue, a carbon-supported quinary PtCuSnWNb high-entropy nanoalloy (denoted as PtCuSnWNb/C) was synthesized by using a polyol reduction method. Due to the unique high-entropy mixing states and strong catalyst-support interactions, PtCuSnWNb/C shows robust structural and compositional stability.

Strong Catalyst-Support Interaction in WOx Nanowires Supported Iridium Nanocatalysts: A Pathway to Efficient Water Electrolysis

This paper investigates the use of sub-stoichiometric tungsten oxide nanowires (WOxNW) as a support material for Ir nanocatalysts in the oxygen evolution reaction (OER) for proton exchange membrane water electrolysis (PEMWE). The results demonstrate that Ir@WOxNW has exceptional activity and durability, which paves the way for large-scale PEMWE deployment. The catalyst-support interaction plays a crucial role in explaining this performance boost.The preparation and characterization of Ir@WOxNW involved loading ultra-fine Ir nanoparticles onto WOxNW through hydrothermal treatment. High-resolution transmission electron microscopy (HR-TEM) and energy-dispersive X-ray spectroscopy (EDS) mapping analysis revealed that the iridium nanoparticles were uniformly loaded on the WOxNW support material, indicating efficient loading and dispersion. X-ray photoelectron spectroscopy (XPS) analysis showed that the supported Ir catalysts had a mixed valence state of Ir0 and Ir4+. Ir@WOxNW was compared with three other Ir-based OER catalysts, outperforming them in terms of activity and durability.The Ir@WOxNW catalyst demonstrated superior OER activity compared to the other three catalysts, with a mass activity of 812 A/gIr at 1.55 V vs reversible hydrogen electrode (RHE). The Tafel slopes of the OER catalysts were grouped into two categories: Ir Black and Ir@WOxNW showed smaller values (about 40 mV/dec), and larger values for Ir@ATO and Ir Oxide (about 120 mV/dec), respectively. Electrochemical impedance spectroscopy (EIS) measurements indicated that the high mass activity of Ir@WOxNW was due to a high population of catalytic sites with fast intrinsic kinetics from the dispersed ultra-fine Ir catalyst on WOxNW. The durability of all catalysts was investigated using an accelerated durability test (ADT), and the Ir@WOxNW catalyst demonstrated unexpectedly high durability compared to the other catalysts.The postmortem XPS analysis showed that the Ir@WOxNW catalyst exhibited a subtle change in Ir0/Ir4+ ratio after the ADT, indicating suppressed Ir oxidation and greater stability compared to the other catalysts. Additionally, non-destructive depth profile analysis by synchrotron based XPS was conducted on the supported ultrafine Ir catalysts before and after the ADT test. The difference in oxidation state increased as the supported Ir catalysts were probed deeper into the core. The results showed that after oxidation potential cycles ADT, the WOxNW-supported Iridium exhibited strong resistance to oxidation. The core location remained a high percentage of metal peak, in contrast to the other three control catalysts.Density functional theory calculations suggested that the oxygen-deficient WOxNW support helps to maintain the OER-active metal@metal oxide core@shell-like form of the Ir catalyst particles by enhancing electron transfer from the WOxNW to the Ir surface, thereby weakening the binding of oxygen to the Ir surface and enhancing the oxidation resistance of the Ir metal to oxides.In conclusion, ultrafine Ir nanoparticles supported on WOxNW have significant potential for practical applications in electrochemical water splitting. The high activity and durability of Ir@WOxNW make it a promising candidate for large-scale PEMWE deployment.

Tungsten Oxide-Based Materials as Catalyst Support for Oxygen Evolution Reaction

The high cost of iridium (Ir) is a major concern for the large scale deployment of polymer electrolyte membrane water electrolysis (PEMWE). To mitigate its impact, the usage of Ir on the anode must be significantly reduced. Down-sizing the catalyst particle is a straight forward strategy but requires the use of appropriate support materials to disperse and anchor fine Ir nanoparticles. We have investigated the use of tungsten oxide-based materials as support for the oxygen evolution reaction (OER) Ir and ruthenium (Ru) catalyst. The synthesis of nanostructured substoichiometric tungsten oxide and the subsequent loading of ultrafine Ir/Ru-based nanoparticles is thoroughly studied. Due to the successful loading, the mass activity of the tungsten oxide-supported Ir/Ru-based catalyst shows significant improvements under rotating disk electrode (RDE) conditions compared with commercially available Ir/Ru-blacks. Furthermore, non-destructive depth profiling by synchrotron-based X-ray photoelectron spectroscopy (XPS) has revealed the strong catalyst-support interaction which suppressed the oxidation of the supported Ir/Ru-based catalysts, leading to much enhanced durability under accelerated durability testing conditions. To verify its performance under practical PEM electrolysis conditions, the tungsten oxide-supported OER catalyst is directly coated onto a polymer electrolyte membrane, i.e., forming a catalyst coated membrane (CCM), and tested under single cell testing conditions without pressure differential. The voltage dependent chemical state of the supported catalyst is also probed in-situ by synchrotron-based XPS where a potential dependent electron transfer between the catalyst and tungsten-oxide support is discovered. Our discovery is anticipated to aid the development of cost effective PEM electrolysis anodes.

Ultrafine Ru nanoparticles on nitrogen-doped CNT arrays for HER: A CVD-based protocol achieving microstructure design and strong catalyst-support interaction

Strong metal-support interactions (SMSIs) play a pivotal role in enhancing the catalytic activity and stability of supported metal catalysts in heterogeneous thermal catalysis, but construction of effective SMSIs remains challenging in electrocatalysis. As a ubiquitous and versatile support for electrocatalysts, carbon materials are generally too inert to generate SMSIs with the loaded metal active sites. We hereby report a CVD-based method to prepare Ru nanoparticles on arrays of oxygen- and nitrogen-doped CNTs grown on the fibers of carbon paper (Ru/ONCNT@CP). The SMSIs were manifested by electronic structure tuning of Ru nanoparticles and their partial embedment in the carbon support. The SMSIs result in optimized Gibbs free energy of H*, lowered energy barrier of H2O dissociation, and enhanced catalyst robustness. Combined with the hierarchical microstructure, high surface area and hydrophilic/aerophobic nature, the Ru/ONCNT@CP electrode displays excellent HER catalytic activity in 1 M KOH, requiring overpotentials of only 73, 180, and 252 mV to achieve current densities of 100, 500, and 800 mA cm−2, respectively. Moreover, the Ru/ONCNT@CP electrode exhibits outstanding stability, with negligible current decay after 120 h HER operation at 100 mA cm−2. This work features an effective and scalable approach for preparation of metal-loaded-carbon electrocatalysts with engineered microstructure and SMSIs.

Promoting photo-Fenton reactions by anchoring Fe doped g-C3N4 onto an amidoxime-functionalized fibrous support for organic contaminants removal

Fe-doped graphitic carbon nitride (g-C3N4) represents an attractive photo-Fenton catalyst for organic contaminants removal, but the practical performances still need to be improved for large-scale application. Herein, we developed a high-efficiency photo-Fenton catalyst by anchoring Fe-g-C3N4 onto an amidoxime-functionalized polyacrylonitrile fiber (AP) substrate through a simple hydrothermal approach. Comprehensive characterizations demonstrate the strong catalyst-support interaction via the axial coordination bonding between -OH groups and Fe3+, which could induce electric polarization of Fe-g-C3N4 to promote the H2O2 adsorption and activation. The fibrous support could also accelerate the photoelectrons transfer from g-C3N4 to Fe3+ by strengthening the d-π conjugated large π bond, as well as alleviate the backflow recombination from Fe3+ to g-C3N4 through the electron sink effect. These synergistic qualities resulted in superior photo-Fenton performance for organic contaminants removal, which delivered 4.0-fold higher degradation kinetics than that of the Fe doped g-C3N4 powder catalyst and exhibited unexpected high activity at strong basic environment (pH = 12). Our work demonstrates an ingenious and simple way to design exceptional photo-Fenton catalysts for environmental remediation.

Electronic Structure of Heteronuclear Cerium-Platinum Clusters.

Beyond the now well-known strong catalyst-support interactions reported for ceria-supported platinum catalysts, intermetallic Ce-Pt compounds exhibit fascinating properties such as heavy fermion behavior and magnetic instability. Small heterometallic Ce-Pt clusters, which can provide insights into the local features that govern bulk phenomena, have been less explored. Herein, the anion photoelectron spectra of three small mixed Ce-Pt clusters, Ce2OPt-, Ce2Pt-, and Ce3Pt-, are presented and interpreted with supporting density functional theory calculations. The calculations, which are readily reconciled with the experimental spectra, suggest the presence of numerous close-lying spin states, including states in which the Ce 4f electrons are ferromagnetically coupled or antiferromagnetically coupled. The Pt center is consistently in a nominal -2 charge state in all cluster neutrals and anions, giving the Ce-Pt bond ionic character. Ce-Pt bonds are stronger than Ce-Ce bonds, and the O atom in Ce2OPt- coordinates only with the Ce centers. The energy of the singly occupied Ce-local 4f orbitals relative to the Pt-local orbitals changes with cluster composition. Discussion of the results includes potential implications for Ce-rich intermetallic materials.

Ordered derivatives on Ti surface enhance the OER activity and stability of Ru-based film electrode

The RuO2 catalytic film electrode with long-term durability is becoming increasingly urgent and challenging for catalysis oxygen evolution reaction (OER). Herein, the Ti-oxides (HxTi2+2xOδ/Ti, HTi/Ti) with ordered porous morphology is derived directly from metallic Ti by using a combination method of hydrothermal and ion exchange, and served as a substrate to support RuO2 catalytic film. The porous HTi plays a wedge-like effect, which significantly improve the adhesion of RuO2 catalytic layer and reducing surface cracks. Moreover, the advanced surface characterization techniques evidence a strong catalyst-support interaction between HTi and RuO2, furtherly enhances the binding strength and modifies the orbital structure of Ru-sites. Electrochemical measurements revealed that the prepared RuO2/HTi/Ti possess a low overpotential of 220 mV and 265 mV to afford the current density of 10 mA cm−2 and 50 mA cm−2, respectively, and exhibits a high mass activity of 1760 ± 60 mA gRu−1 at overpotential of 290 mV. Accelerated life test confirmed the robust durability of RuO2/HTi/Ti, which can run stably for up to 11 h at 500 mA cm−2 current density with a low mass loading of 0.1 mg cm−2. The remarkable OER performance is closely associated with the ordered porous HTi and interfacial interactions, which demonstrate the surface engineering to create ordered derivative layers directly from the substrate is important to improve the activity and stability of catalytic film electrode.

Activity-Stability Balance: The Role of Electron Supply Effect of Support in Acidic Oxygen Evolution.

Developing efficient and durable electrocatalysts for the oxygen evolution reaction (OER) in proton exchange membrane (PEM) electrolyzers represents a significant challenge. Herein, the cobalt-ruthenium oxide nano-heterostructures are successfully synthesized on carbon cloth (CoOx /RuOx -CC) for acidic OER through a simple and fast solution combustion strategy. The rapid oxidation process endows CoOx /RuOx -CC with abundant interfacial sites and defect structures, which enhances the number of active sites and the charge transfer at the electrolyte-catalyst interface, promoting the OER kinetics. Moreover, the electron supply effect of the CoOx support allows electrons to transfer from Co to Ru sites during the OER process, which is beneficial to alleviate the ion leaching and over-oxidation of Ru sites, improving the catalyst activity and stability. As a self-supported electrocatalyst, CoOx /RuOx -CC displays an ultralow overpotential of 180mV at 10mAcm-2 for OER. Notably, the PEM electrolyzer using CoOx /RuOx -CC as the anode can be operated at 100mAcm-2 stably for 100h. Mechanistic analysis shows that the strong catalyst-support interaction is beneficial to redistribute the electronic structure of RuO bond to weaken its covalency, thereby optimizing the binding energy of OER intermediates and lowering the reaction energy barrier.

WOx nanowire supported ultra-fine Ir-IrOx nanocatalyst with compelling OER activity and durability

Ultra-fine iridium (Ir) nanocatalyst is successfully dispersed and stabilized on sub-stoichiometric tungsten oxide nanowires (WOxNW) forming an active and stable OER catalyst. With its abundant amount of exposed active surfaces, the WOxNW supported Ir catalyst shows a high mass activity of 812 A/gIr at 1.55 V vs RHE. This value is three times higher than Ir-black and 30 times higher than Ir supported on antimony-doped tin oxide. The Ir@WOxNW possesses much satisfactory stability, showing a loss of only 40 % compared with the nearly 100 % loss of Ir-black after 1,000 accelerated durability testing cycles. Non-destructive depth profile by synchrotron-based XPS and density functional calculations unambiguously reveal the strong catalyst-support interaction between the WOxNW and the supported Ir catalyst. Due to the inhibited oxidation, the OER active core–shell-like structure of the Ir-IrO2 is well-maintained on the WOxNW supports under OER testing conditions. The developed catalyst shows high potential to significantly reduce Ir usage for practical water electrolysis.

Strategies of Anode Design for Seawater Electrolysis: Recent Development and Future Perspective

Compared with freshwater splitting, seawater electrolysis has more spaces to be explored, which is primarily attributed to the additional critical catalytic challenges of the competition between anodic oxygen evolution reaction (OER) and chlorine chemistry, deep corrosion, and site blocking due to the presence of chloride ions and insoluble particulate in seawater. However, if direct seawater electrolysis can be realized, it would revolutionize the energy and environmental sectors. In this review, the current effective strategies are summarized, including electronic modulation, oxygen vacancies creation, amorphous and porous structure design, corrosion‐resistant passive layer decoration, and creating strong catalyst–support interactions. The review also provides insights for seawater electrolysis on rational design of the OER catalyst with high selectivity, activity, corrosion resistance, chemical, and mechanical durability. Beyond the progress made to date, a perspective in the fabrication of high‐performance anodes for direct seawater electrolysis is also proposed. Collectively, this review will shed light on the rational design of a viable anode for massive and sustainable hydrogen fuel production from immense seawater.

In‐situ nano‐engineering of amorphous MoS 2 nanosheets with carbon dots for enhanced supercapacitor performances

Amorphous materials have snatched special attention for electrochemical energy storage applications owing to the presence of plenty of activate sites for energy storage. Herein, we report the microwave-assisted-hydrothermal synthesis of amorphous MoS2 with some 1T phase and in-situ-nano-engineering with C-dots for energy storage application. The specific capacitance (Cs) of a-MoS2/C-dots was found to be 1368 F g−1 (at 1 A g−1), which is ∼ 2.9 and 1.65 times higher than a-MoS2 (without C-dots) and crystalline c-MoS2/C-dots. Capacitance is also strongly dependent on synthesis methods: Cs of a-MoS2/C-dots is 2.15 times higher than h-MoS2/C-dots produced by the normal-hydrothermal method. The asymmetric supercapacitor was designed using a-MoS2/C-dots as cathode and activated-carbon as anode showing Cs 180.82 F g−1 at a maximum potential of 1.5 V. Energy density (ED) of 56.5 W h kg−1 at a power density (PD) of 750 W kg−1 with excellent capacitance retention was observed. The high Cs of a-MoS2/C-dots can be attributed to amorphous MoS2, formation of metallic 1T phase, good charge transport, and strong catalyst support interaction. This synthesis and in-situ nano engineering method of MoS2 may provide a promising technique for developing a high-performance supercapacitor for energy storage applications.

A general strategy for heterogenizing olefin polymerization catalysts and the synthesis of polyolefins and composites

The heterogenization of homogeneous metal complexes on solid supports presents an efficient strategy for bridging homogeneous catalysts with industrially-preferred heterogeneous catalysts; however, a series of drawbacks restrict their implementation in olefin polymerization, particularly for copolymerization with polar comonomers. In this contribution, we report an ionic anchoring strategy that is highly versatile, generally applicable to different systems, and enables strong catalyst-support interactions while tolerating various polar functional groups. In addition to greatly enhanced polymerization properties, the supported catalysts achieved higher comonomer incorporation than their unsupported counterparts. This strategy enabled efficient polymerization at high temperatures at large scale and great control over product morphology, and the facile synthesis of polyolefin composites. More importantly, the dispersion of different fillers in the polyolefin matrix produced great material properties even at low composite loadings. It is expected that this strategy will find applications in different catalytic systems and the synthesis of advanced engineering materials.

Bifunctional WC‐Supported RuO2 Nanoparticles for Robust Water Splitting in Acidic Media

AbstractWe report the strong catalyst–support interaction in WC‐supported RuO2 nanoparticles (RuO2‐WC NPs) anchored on carbon nanosheets with low loading of Ru (4.11 wt.%), which significantly promotes the oxygen evolution reaction activity with a η10 of 347 mV and a mass activity of 1430 A gRu−1, eight‐fold higher than that of commercial RuO2 (176 A gRu−1). Theoretical calculations demonstrate that the strong catalyst–support interaction between RuO2 and the WC support could optimize the surrounding electronic structure of Ru sites to reduce the reaction barrier. Considering the likewise excellent catalytic ability for hydrogen production, an acidic overall water splitting (OWS) electrolyzer with a good stability constructed by bifunctional RuO2‐WC NPs only requires a cell voltage of 1.66 V to afford 10 mA cm−2. The unique 0D/2D nanoarchitectures rationally combining a WC support with precious metal oxides provides a promising strategy to tradeoff the high catalytic activity and low cost for acidic OWS applications.

Bifunctional WC‐Supported RuO2 Nanoparticles for Robust Water Splitting in Acidic Media

AbstractWe report the strong catalyst–support interaction in WC‐supported RuO2 nanoparticles (RuO2‐WC NPs) anchored on carbon nanosheets with low loading of Ru (4.11 wt.%), which significantly promotes the oxygen evolution reaction activity with a η10 of 347 mV and a mass activity of 1430 A gRu−1, eight‐fold higher than that of commercial RuO2 (176 A gRu−1). Theoretical calculations demonstrate that the strong catalyst–support interaction between RuO2 and the WC support could optimize the surrounding electronic structure of Ru sites to reduce the reaction barrier. Considering the likewise excellent catalytic ability for hydrogen production, an acidic overall water splitting (OWS) electrolyzer with a good stability constructed by bifunctional RuO2‐WC NPs only requires a cell voltage of 1.66 V to afford 10 mA cm−2. The unique 0D/2D nanoarchitectures rationally combining a WC support with precious metal oxides provides a promising strategy to tradeoff the high catalytic activity and low cost for acidic OWS applications.

Very strong interaction between FeN4 and titanium carbide for durable 4-electron oxygen reduction reaction suppressing catalyst deactivation by peroxide

Very strong catalyst–support interaction was realized by supporting FePc with Ti3C2, encouraging biased electron transfer to Fe. 4e ORR activity was improved to suppress peroxide production and therefore to have ORR durability guaranteed.

High-density ultrafine RuP2 with strong catalyst-support interaction driven by dual-ligand and tungsten-oxygen sites for hydrogen evolution at 1 A cm−2

Ultrafine and high-density RuP2 based on coordination chemistry and catalyst-support correlation shows potential for hydrogen evolution reaction (HER). Herein, the uniform and high-density W-doped ultra-small RuP2 (W0.05-RuP2@C3N4-NC) are synthesized by incorporating oxygen-bridged [WO4] tetrahedron into tetraacetic acid (EDTA)-melamino-formaldehyde (MF) ligands. EDTA-MF shows strong metal-support interaction, dedicating to the optimal dispersion, highest Ru yields, and HER activity. W atoms regulate local electron structure and coordination environment, leading to faster proton supply and hydrogen release, thus achieving 10 mA cm−2 at low overpotential of 27 mV (alkaline) and 66 mV (acidic). Notably, W0.05-RuP2@C3N4-NC maintains stability with staged 500–1000 mA cm−2 for 1000 h in alkaline, and 1000 mA cm−2 for ~300 h in acid, ascribing to the immobilized ultra-stable RuP2 nanoclusters via EDTA-MF and metal-oxygen sites. The excellent activity and stability hold promise for industrial hydrogen production, which provides deeper insights into catalyst-support interaction and reasonable design of high Ru-loading electrocatalysts.

Accelerated N2 reduction kinetics in hybrid interfaces of NbTiO4 and nitrogen-doped carbon nanorod via synergistic electronic coupling effect

Electrochemical ammonia synthesis through the atmospheric nitrogen reduction reaction (NRR) is a promising method for sustainable fertilizer and carbon-free hydrogen energy carriers. The inevitable selectivity gap against hydrogen evolution reaction and inert nitrogen (N2) hinders the device-level usage of nitrogen cathodes. In this work, we report engineered electrocatalyst/support interface of NbTiO4 nanoparticles supported on nitrogen-doped carbon nanorods (NbTiO4@NCNR) to catalyze NRR. Insisted by the pitfalls to rationally design N2 reduction catalysts, the strong catalyst-support interaction strategy is adapted to tune the selectivity towards NRR. Electrochemical tests reveal that NbTiO4@NCNR hybrid accelerates a 10-fold increase in N2 selectivity compared to pure metal oxide. Using first-principles calculations, we identify the underlying mechanism of enhanced performance: bridging bonds in the interface as electron transport channels to promote the N2 reduction kinetics. Essentially, this study provides an insight into how to overcome the immense kinetic barrier of NRR using smartly engineered interfaces of hybrid materials.

Rational design of CdCO3 nanoparticles decorated carbon nanofibers for boosting electrochemical CO2 reduction

Efficient, robust and inexpensive catalysts are highly desirable to drive the electrochemical CO2 reduction reaction (CO2RR) to value-added fuels. Herein, low-cost CdCO3 nanoparticles (NPs) decorated carbon nanofibers (CdCO3-CNFs) were synthesized by a facile one-pot method to boost the performance of CO2RR to CO. The obtained CdCO3-CNFs show a high Faradaic efficiency (93.4%) and a good partial current density (~10 mA cm−2) at a potential of −0.83 V. Moreover, CdCO3-CNFs achieve high CO production rates at moderately negative potentials and a good stability of 24 h with negligible degradation. The superior performance is attributed to the increased number of catalytically active sites, and the strong interaction between CdCO3 NPs and CNFs which promotes electron transfer and secures active sites. This study provides a promising strategy for the efficient and durable CO2RR by designing a carbonate/carbon system with a strong catalyst-support interaction.

Strong catalyst support interactions in defect-rich γ-Mo2N nanoparticles loaded 2D-h-BN hybrid for highly selective nitrogen reduction reaction

Electrochemical ammonia synthesis by N2 fixation has proven to be a promising alternative to the energy-consuming, befouling Haber-Bosch process. Considering the low faradaic efficiency and sluggish kinetics of Nitrogen Reduction Reaction (NRR), it is significant to design a robust and selective catalyst. Herein, we demonstrate a single step in-situ nitridation method to grow cubic molybdenum nitride (γ-Mo2N) nanoparticles on a 2D hexagonal boron nitride (h-BN) sheets as a potential, cost-effective electrocatalyst for NRR, in which the selectivity for N2 was regulated by interfacially engineering the Mo2N-BN bridge. The maneuverability of h-BN sheets enabled the provocation of N-vacancies governed by the particle size, where the fine-tuning of their significance emanated the highest faradaic efficiency of 61.5 %. Moreover, such non-noble metal-based hybrids delivered a stable performance for 20 h. Therefore, our approach of designing the electronic structure of a catalyst by controlling the defects could be an effective practice for selective NRR.