N2 Reduction Reaction Performance Research Articles

Defect Engineering in Bi-Based Photo/Electrocatalysts for Nitrogen Reduction to Ammonia.

Main group Bi-based materials have gained popularity as N2 reduction reaction (NRR) photo/electrocatalysts due to their ability to inhibit competitive H2 evolution reactions (HER) and the unique N2 adsorption activities. The introduction of defects in Bi-based catalysts represents a highly effective strategy for enhancing light absorption, promoting efficient separation of photogenerated carriers, optimizing the activity of free radicals, regulating electronic structure, and improving catalytic performance. In this review, we outline the various applications of state of the defect engineering in Bi-based catalysts and elucidate the impact of vacancies on NRR performance. In particular, the types of defects, methods of defects tailoring, advanced characterization techniques, as well as the Bi-based catalysts with abundant defects and their corresponding catalytic behavior in NRR were elucidated in detail. Finally, the main challenges and opportunities for future development of defective Bi-based NRR catalysts are discussed, which provides a comprehensive theoretical guidance for this field.

Boosting Electrochemical Nitrogen Reduction via Axial Coordination Engineering on Single‐Iron‐Atom Catalysts

AbstractElectrocatalytic nitrogen (N2) reduction reaction (NRR) presents a sustainable alternative to the Haber–Bosch process for ammonia (NH3) synthesis. Iron phthalocyanine (FePc) is demonstrated as a promising catalyst for the electrocatalytic NRR. However, FePc with planar symmetric Fe‐N4 sites exhibits poor N2 adsorption and activation capabilities, resulting in an unsatisfactory NRR performance. Herein, an axial oxygen coordination strategy is developed to optimize the local electron distribution on FePc for improving N2 adsorption and activation. The as‐obtained FePc‐O‐CP shows a superior NH3 yield rate (59.72 µg h−1 mg−1cat.) and a considerable Faradaic efficiency (13.76%) in 0.1 m HCl. Density functional theory (DFT) calculations verify that the axial oxygen ligand on FePc inhibits the adsorption of H+ and enhances the N2 adsorption and activation, thereby greatly promoting NH3 generation. This work reveals the significance of regulating the local coordination environment of single‐atom catalysts for improving electrocatalytic NRR performance and provides a feasible strategy for the rational design of atomic‐scale active sites.

High throughput screening for electrocatalysts for nitrogen reduction reaction using metal-doped bilayer borophene: A combined approach of DFT and machine learning

NH3 plays an important role in industrial production, while it is still a challenge to develop a promising catalyst for NH3 synthesis. In particular, the metal borides have attracted much attention because of their excellent catalyst performances towards N2. In this paper, we have theoretically studied the N2 reduction reaction (NRR) by employing the transition metal (TM = Co, Cr, Cu, Fe, Mn, Mo, Ni, Sc, Ti, V, Zn, Nb, Pd, Rh, Ru or Zr) doped bilayer borophene (BB). After the screening, it is found that Sc-doped BB (Sc@BB) exhibits excellent NRR performance with the limiting potential of -0.43 V, and the hydrogen evolution reaction (HER) could be well suppressed. The limiting potential could be further improved into -0.40 V by applying 0.30 % uniaxial strains to the system. In addition, the machine learning method was employed to understand the catalytic mechanism, the results revealed that the NRR performance of TM@BB is strongly related to the inherent properties of TM atoms, such as the d-electron number, electronegativity, first ionization energy, atomic radius, and atomic number. Therefore, our paper not only proposed a promising electrocatalyst for NRR, but also further extend the application of transition metal-boron based two dimensional materials in NRR.

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.

Transition metal doped and strain engineered VS−MoS2 as electrocatalysts for N2 electroreduction: A DFT study

S vacancy activated MoS2 (VS−MoS2) materials are greatly attractive as electrocatalysts in electrocatalytic N2 reduction reaction (NRR). Herein, we investigate the electrocatalytic NRR performance of transition metal (Cr, Mn, V, W) doped and strain engineered VS−MoS2 using first-principles calculations. For all the designed MoS2s, VS is easy to form due to the small defect formation energy (≤3.48 eV) and determined as active site for N2 adsorption and electrocatalytic NRR. Calculation results show that doping and strain regulate the electrocatalytic activity of VS−MoS2 by altering its electronic properties. When strain is absent, Cr-, Mn-, and V-VS−MoS2 exhibit better electrocatalytic NRR activity than undoped VS−MoS2, while W-VS−MoS2 shows slightly worse activity. However, the above situation changes with applying strain. Moreover, the catalytic activity of all the catalysts firstly decreases and then increases with increasing strain. Further comprehensive considering limiting potential (UL) and Faraday efficiency (FE), Cr-VS−MoS2 under 7 % strain is identified as the best NRR electrocatalyst with both excellent activity (UL = -0.18 V) and high selectivity (FE = 99.44 %). In addition, 5 % and 6 % strained Mn-VS−MoS2 are also good electrocatalysts for NRR with low UL and (-0.45 V and -0.23 V, respectively) and substantial FE (37.69 % and 19.29 %, respectively). Therefore, the electrocatalytic NRR performance of VS−MoS2 could be optimized through transition metal doping and strain engineering. Relevant experimental explores will be encouraged based on our theoretical findings.

Boosting protonation kinetics for ammonia electrosynthesis on Ru sites embedded in nanoporous ReSe2

Electrocatalytic N2 reduction reaction (NRR) is a promising approach for renewable NH3 production but is constrained by poor activity and selectivity, owing to the sluggish hydrogenation kinetics. Herein, we prepare a nanoporous Ru-doped ReSe2 (NP Ru-ReSe2) with controllable selenium vacancies by regulating the amount of Ru dopants. The catalyst exhibits excellent the NRR performance, which affords a high Faradaic efficiency of 22.7% and NH3 yield rate of 19.41 μg h−1 mg−1 at –0.4 V versus a reversible hydrogen electrode(RHE). In situ attenuated total reflectance–surface-enhanced infrared absorption spectroscopy studies combined with theoretical calculations unravel that a clear synergistic effect of Ru dopants and selenium vacancies onregulating the proton (H*) coverage on the ReSe2 surface to accelerate the proton-coupled processes as NN → NNH. while N2 dissociation becomes exothermic over the Ru active sites via Ru-to-N2 π back-donation, lowering energy barriers of the rate-determining step, ultimately enhancing the overall NRR catalytic performance.

Preparation of Cu atom doped LaFeO3/activated porous carbon composites and their electrocatalytic nitrogen reduction performance

The electrocatalytic N2 reduction reaction (NRR) under ambient conditions is a green and sustainable method for ammonia (NH3) synthesis, and the development of efficient electrocatalysts for NRR is a top priority. In recent years, LaFeO3 has been widely used in the field of catalysis because of its high stability, low cost, and green advantages. Through strategies such as heteroatom doping and carbon loading, we can effectively increase the content of oxygen vacancies and improve the electrical conductivity of the material to produce composites with unique electronic structures and excellent catalytic properties. In the present work, we prepared single-atom doped LaFeO3/activated porous carbon composites (LFC/AC) for electrocatalytic NRR. The NH3 yield and Faraday efficiency of LFC/AC were the highest at 23.876 μg h−1 mg−1 and 6.53% in 0.1 M Na2SO4 electrolyte solution, both of which were higher than those of LFC. A series of characterizations and tests have shown that LFC/AC has excellent stability, electrical conductivity, and electrocatalytic properties. The density flooding theory (DFT) simulations were performed to explore the main mechanisms to improve the NRR performance of the materials.

Effects of Molybdenum Doping on the Enhanced Electrocatalytic Nitrogen Reduction Reaction Performance of CeO2 Nanorods: Theoretical and Experimental Investigations.

As a green and sustainable strategy, the electrocatalytic N2 reduction reaction (NRR) has been considered the best potential approach to replace the traditional Haber-Bosch process under ambient conditions. The key is to exploit efficient and low-cost electrocatalysts according to the current situation. Herein, a series of Molybdenum (Mo) doped CeO2 nanorods (NR) catalysts were successfully fabricated via a hydrothermal reaction coupled with high temperature calcination. The nanorod structures were not altered after Mo atom doping. The obtained 5 %-Mo-CeO2 nanorods act as a superior electrocatalyst in neutral electrolytes of 0.1 M Na2 SO4 . Such electrocatalyst significantly enhances NRR performance with an NH3 yield of 10.9 μg h-1 mg-1 cat at -0.45 V vs reversible hydrogen electrode (RHE) and a Faradaic efficiency (FE) of 26.5 % at -0.25 V vs RHE. That outcome is 4 times higher than that of CeO2 nanorods (2.6 μg h-1 mg-1 cat ; 4.9 %). Meanwhile, density functional theory (DFT) calculation shows the characteristics after Mo doping: the band gap value lowers, the density of states increases, electrons are more easily excited, and N2 molecules are more easily adsorbed, thereby enhancing the activity of the electrocatalytic NRR.

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Atomically Dispersed Sn Protuberance.

Atomically dispersed metal catalysts show potential advantages in N2 reduction reaction (NRR) due to their excellent activity and efficient metal utilization. Unfortunately, the reported catalysts usually exhibit unsatisfactory NRR activity due to their poor N2 adsorption and activation. Herein, we report a novel Sn atomically dispersed protuberance (ADP) by coordination with substrate C and O to induce positive charge accumulation on Sn site for improving its N2 adsorption, activation and NRR performance. The extended X-ray absorption fine structure (EXAFS) spectra confirmed the local coordination structure of the Sn ADPs. NRR activity was significantly promoted via Sn ADPs, exhibiting a remarkable NH3 yield (RNH3 ) of 28.3 μg h-1 mgcat -1 (7447 μg h-1 mgSn -1 ) at -0.3 V. Furthermore, the enhanced N2 Hx intermediates was verified by in situ experiments, yielding consistent results with DFT calculation. This work opens a new avenue to regulate the activity and selectivity of N2 fixation.

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Atomically Dispersed Sn Protuberance

AbstractAtomically dispersed metal catalysts show potential advantages in N2 reduction reaction (NRR) due to their excellent activity and efficient metal utilization. Unfortunately, the reported catalysts usually exhibit unsatisfactory NRR activity due to their poor N2 adsorption and activation. Herein, we report a novel Sn atomically dispersed protuberance (ADP) by coordination with substrate C and O to induce positive charge accumulation on Sn site for improving its N2 adsorption, activation and NRR performance. The extended X‐ray absorption fine structure (EXAFS) spectra confirmed the local coordination structure of the Sn ADPs. NRR activity was significantly promoted via Sn ADPs, exhibiting a remarkable NH3 yield (RNH3) of 28.3 μg h−1 mgcat−1 (7447 μg h−1 mgSn−1) at −0.3 V. Furthermore, the enhanced N2Hx intermediates was verified by in situ experiments, yielding consistent results with DFT calculation. This work opens a new avenue to regulate the activity and selectivity of N2 fixation.

To Molecularly Block Hydrogen Evolution Sites of Molybdenum Disulfide toward Improved Catalytic Performance for Electrochemical Nitrogen Reduction.

2H-molybdenum disulfide (2H-MoS2 ) represents a classical catalyst for the electrochemical N2 reduction reaction (NRR) in water that offers a promising technology toward sustainable production of NH3 driven by renewable energy. While the catalytic efficiency is severely limited by a simultaneous and competing H2 evolution reaction (HER). Herein, it is proposed that the S edge of 2H-MoS2 , which is known as main sites to afford HER, is intentionally covered by cobalt phthalocyanine (CoPc) molecules through axial coordination. While the Mo sites with S vacancies at 2H-MoS2 edge is recognized as highly NRR active, and can keep structurally intact in the CoPc based modification. The resultant composite thus exhibits high NRR performance with Faradic efficiency and NH3 yields increase by fourfold and twofold, respectively, comparing to pristine 2H-MoS2 . These findings provide a deep insight into the mechanism of 2H-MoS2 based NRR catalysis and suggest an efficient molecular modification strategy to promote NRR in water.

High-throughput screening of B/N-doped graphene supported single-atom catalysts for nitrogen reduction reaction

Transitional metal single atom (TM1) doped graphene catalysts have been widely applied in electrochemical N2 reduction reaction (NRR). However, it remains a challenge for the rational design of highly active and selective electrocatalysts owing to limited knowledge of structure-activity correlations. Here, we adopted first-principle calculations to high-throughput screen the NRR performance of TM1 coordinated with two boron and two nitrogen atoms in graphene (TM1-B2N2/G). A “five-step” strategy was implemented by progressively considering different metrics such as stability, N2 adsorption, N2 activation, potential-determining step, and selectivity. As a result, a volcano plot of reactivity is established by using the valence electron number of TM1 as the descriptor. Among all catalysts, Cr1-B2N2/G exhibits superior performance with a limiting potential of -0.43 V with high selectivity of NRR interpreted by better spatial symmetry and excellent compatibility in terms of energy when N2 interacts with TM1. Our work reveals the general strategy of computational efforts to predict the next generation of advanced catalytic materials for NRR.

Boosting Electrocatalytic Ammonia Synthesis of Bio-Inspired Porous Mo-Doped Hematite via Nitrogen Activation.

Electrochemical N2 reduction reaction (NRR) emerges as a highly attractive alternative to the Haber-Bosch process for producing ammonia (NH3) under ambient circumstances. Currently, this technology still faces tremendous challenges due to the low ammonia production rate and low Faradaic efficiency, urgently prompting researchers to explore highly efficient electrocatalysts. Inspired by the Fe-Mo cofactor in nitrogenase, we report Mo-doped hematite (Fe2O3) porous nanospheres containing Fe-O-Mo subunits for enhanced activity and selectivity in the electrochemical reduction from N2 to NH3. Mo-doping induces the morphology change from a solid sphere to a porous sphere and enriches lattice defects, creating more active sites. It also regulates the electronic structures of Fe2O3 to accelerate charge transfer and enhance the intrinsic activity. As a consequence, Mo-doped Fe2O3 achieves effective N2 fixation with a high ammonia production rate of 21.3 ± 1.1 μg h-1 mgcat.-1 as well as a prominent Faradaic efficiency (FE) of 11.2 ± 0.6%, superior to the undoped Fe2O3 and other iron oxide catalysts. Density functional theory (DFT) calculations further unravel that the Mo-doping in Fe2O3 (110) narrows the band gap, promotes the N2 activation on the Mo site with an elongated N≡N bond length of 1.132 Å in the end-on configuration, and optimizes an associative distal pathway with a decreased energy barrier. Our results may pave the way toward enhancing the electrocatalytic NRR performance of iron-based materials by atomic-scale heteroatom doping.

First Principles Study of Double Boron Atoms Supported on Graphitic Carbon Nitride (g-C3N4) for Nitrogen Electroreduction

Electrocatalytic reduction of N2 provides a clean, sustainable way for NH3 production. Efficient catalysts thus play a key role but remain a long-term challenge. In this study, the catalytic activity of double boron supported on graphitic carbon nitride (g-C3N4) for a N2 reduction reaction (NRR) is explored by density functional theory (DFT) calculations. Our results show that double boron atoms embedded in g-C3N4 with coordination of four N atoms and two boron atoms exhibits an excellent NRR performance with negligible energy consumption for adding hydrogen to *N2, while a moderate ΔG of 0.58 eV for the formation of the second NH3 suggests this catalyst is a potential candidate for N2 fixation.

A‐Site Substitution Motivating the Phase Transformation of LaNiO3 Perovskite for High‐Performance Artificial N2 Fixation

AbstractElectrocatalytic N2 reduction reaction (NRR) to NH3 under ambient conditions is an attractive strategy compared to the traditional Haber‐Bosch process. However, there still remains a great challenge due to the high activation barrier of N2 and consequent sluggish kinetics. Herein, A‐site substitution of LaNiO3 perovskites by Sr‐doping is proposed which can lead to phase transformation and to the formation of oxygen vacancies, significantly improving the NRR performance of La1‐xSrxNiO3 (LSNO). The appropriate oxygen vacancy concentration can be modulated by changing the stoichiometric ratio of La and Sr elements. LSNO‐III (x=0.5) delivers the highest ammonia production rate of 55.9 μg h−1 mg−1cat. at −0.7 V and Faraday efficiency of 23.17 % at −0.5 V versus the reversible hydrogen electrode in 0.1 M Na2SO4. Density functional theory (DFT) calculations further demonstrate that introduction of oxygen vacancies decreases the distance of the d‐band center to the Fermi energy level, which not only facilitates adsorption and activation of N2 molecules and subsequent hydrogenation reactions, but also further optimizes reaction pathways in NRR.

Atomic-Scale Homogeneous RuCu Alloy Nanoparticles for Highly Efficient Electrocatalytic Nitrogen Reduction.

Ruthenium (Ru) is the most widely used metal as an electrocatalyst for nitrogen (N2 ) reduction reaction (NRR) because of the relatively high N2 adsorption strength for successive reaction. Recently, it has been well reported that the homogeneous Ru-based metal alloys such as RuRh, RuPt, and RuCo significantly enhance the selectivity and formation rate of ammonia (NH3 ). However, the metal combinations for NRR have been limited to several miscible combinations of metals with Ru, although various immiscible combinations have immense potential to show high NRR performance. In this study, an immiscible combination of Ru and copper (Cu) is first utilized, and homogeneous alloy nanoparticles (RuCu NPs) are fabricated by the carbothermal shock method. The RuCu homogeneous NP alloys on cellulose/carbon nanotube sponge exhibit the highest selectivity and NH3 formation rate of ≈31% and -73μmol h-1 cm-2 , respectively. These are the highest values of the selectivity and NH3 formation rates among existing Ru-based alloy metal combinations.

An integrated Si photocathode with lithiation-activated molybdenum oxide nanosheets for efficient ammonia synthesis

As an alternative to the conventional industrial Haber-Bosch process, photoelectrochemical (PEC) routes that are powered by renewable solar energy hold great promise for N2 reduction reaction (NRR) towards NH3 synthesis at ambient conditions. However, great challenges remain in promoting NH3 production rate for the PEC NRR devices, especially with the earth-abundant catalysts. Here we report an integrated LixMoO3/n+np+-Si photocathode could achieve an unprecedented PEC NH3 yield rate of 8.7 μg cm−2 h−1, which is among the highest PEC NRR systems ever reported. With an optically and electrocatalytically decoupled configuration, the integrated PEC photocathode could harvest the sunlight sufficiently and simultaneously promote the catalytic kinetics, thus leading to the improved NH3 synthesis. More importantly, such high PEC NRR performance is derived from earth-abundant elements without precious noble metals. Verified by the electrochemical experiments and density functional theory (DFT) calculations, the lithiation strategy gives rise to dramatic structural distortion accompanying the abundant oxygen vacancies and Mo5+ ions, which results in faster NRR kinetics and activates inert MoO3 into efficient LixMoO3 electrocatalyst towards NH3 synthesis. This work holds great promise in constructing monolithic PEC device to directly harvest solar light for artificial ammonia photosynthesis.

Single Nb atom modified anatase TiO2(110) for efficient electrocatalytic nitrogen reduction reaction

We report the theory-guided design of anatase-supported Nb catalysts for electrochemical N 2 reduction reaction (NRR). Theoretical calculations predict that Nb atoms deliver multi-functional enhancement toward the NRR when incorporated in an anatase TiO 2 (110) catalyst: (1) decreasing the band gap and inducing electrons to promote the conductivity of TiO 2 (110); (2) suppressing the undesired competitive hydrogen evolution reaction; (3) activating the inert Ti sites for N 2 adsorption; (4) enabling fast charge transfer between ∗NNH and the TiO 2 (110) surface; and (5) reducing the energy barrier of the potential-determining ∗N 2 → ∗NNH step, further facilitating NH 3 formation. As a result, our Nb-TiO 2 (110) catalyst exhibits superior activity and selectivity for the NRR, which affords an NH 3 production rate of about 21.3 μg h −1 mg cat −1 and NH 3 faradaic efficiency of ∼9.2% at −0.5 V (versus reversible hydrogen electrode). This study provides insights for the rational design of efficient electrocatalysts for the NRR. • Nb single-atom-decorated TiO 2 (110) facilitates nitrogen reduction reaction (NRR) • TiO 2 (110) is more active than TiO 2 (101) for NRR • Nb-TiO 2 (110) delivers an NH 3 production rate of ∼21.3 μg h −1 mg cat −1 • Single Nb atom modified anatase TiO 2 (110) for efficient electrocatalytic nitrogen reduction reaction An electrochemical N 2 reduction reaction (NRR) that can be powered by electricity generated from renewable sources has recently gained heightened research interest, providing a promising alternative to the conventional Haber-Bosch process. Current major research efforts are being devoted to the design and development of advanced electrocatalysts to enhance the efficiency of NRR. Herein, guided by density functional theory calculations that predict the cooperative effect of Nb and anatase TiO 2 (110) in promoting electrocatalytic NRR performance, we successfully synthesize TiO 2 single crystals with selectively exposed (110) facets, supplemented with Nb atomic loading, which exhibited remarkable performance for NRR, achieving an NH 3 production rate of ∼21.3 μg h −1 mg cat −1 at −0.5 V (versus reversible hydrogen electrode). Ammonia is extensively used in industry, agriculture, and energy storage. Currently, the industrial synthesis of ammonia predominantly still relies on the energy- and capital-intensive Haber-Bosch (HB) process. Electrochemical N 2 reduction reaction (NRR) provides a renewable and distributed route for ammonia production. To boost the NRR, the development of electrocatalysts is key. Herein, we design and synthesize Nb single-atom-decorated anatase TiO 2 (110) for enhanced NRR, affording an NH 3 production rate of ∼21.3 μg h −1 mg cat −1 .

Rational design of highly efficient electrocatalytic single-atom catalysts for nitrogen reduction on nitrogen-doped graphene and g-C2N supports

Electrochemical N2 reduction reaction (NRR) is a very attractive route for ammonia production under ambient conditions. It is a challenging issue to develop efficient electrocatalysts in NRR process. Herein, we designed a series of NRR single-atom catalysts (SACs), namely, transition metal single-atom anchored on nitrogen-doped porous graphene with six-fold N6 cavity (TM@N6-G). Based on spin-polarized density functional theory (DFT) calculations, the stability and catalytic performance of TM@N6-G SACs were systemically investigated. Six promising catalysts (Nb, Mo, Tc, Ta, W, and Re@N6-G) are selected from 14 candidates by screening the free energy changes of the first and last electric chemical steps. Detailed NRR mechanism studies show that the six SACs have superior electrochemical NRR performance, especially W@N6-G, reaching low limiting potentials of −0.23 V. Furthermore, we extend the present study to another kind of graphitic carbon nitrides, g-C2N, which has a similar N6 cavity. Our calculations show that five TM@g-C2N SACs have good stability and high activity and selectivity for NRR. In addition, ΔG*NNH, dN-N, and ICOHP can be used as descriptors to understand the origin of NRR catalytic activity of these two kinds of catalysts. The present work may provide valuable clues for exploring promising and efficient NRR electrochemical catalysts.

MXene Quantum Dots/Copper Nanocomposites for Synergistically Enhanced N2 Electroreduction

Electrocatalytic N2 reduction reaction (NRR) represents an appealing solution for sustainable ammonia production, whereas exploring high‐efficiency NRR catalysts is highly desired but extremely challenging. Herein, we combine Ti3C2Tx‐MXene quantum dots (MQDs) with porous Cu nanosheets to design a novel heterostructured MQDs/Cu as an effective and durable NRR catalyst. Impressively, MQDs/Cu showed a synergistically enhanced NRR activity with an NH3 yield of 78.5 μg h−1 mg−1 (−0.5 V) and a Faradaic efficiency of 21.3% (−0.4 V), far superior to pure MQDs and Cu, and outperforming the majority of the state‐of‐the‐art NRR catalysts. Density function theory computations demonstrated that the synergy of MQDs and Cu enabled the creation of interfacial Cu‐Ti dimer as dual‐active‐centers to strongly activate the absorbed N2 and promote the *N2H formation, consequently resulting in the much reduced energy barriers and greatly enhanced NRR performance.