Zn Single-Atom Catalysts Enable the Catalytic Transfer Hydrogenation of α,ß-Unsaturated Aldehydes.

Highly active nonprecious-metal single-atom catalysts (SACs) toward catalytic transfer hydrogenation (CTH) of α,ß-unsaturated aldehydes are of great significance but still are deficient. Herein, we report that Zn-N-C SACs containing Zn-N3 moieties can catalyze the conversion of cinnamaldehyde to cinnamyl alcohol with a conversion of 95.5% and selectivity of 95.4% under a mild temperature and atmospheric pressure, which is the first case of Zn-species-based heterogeneous catalysts for the CTH reaction. Isotopic labeling, in situ FT-IR spectroscopy, and DFT calculations indicate that reactants, coabsorbed at the Zn sites, proceed CTH via a "Meerwein-Ponndorf-Verley" mechanism. DFT calculations also reveal that the high activity over Zn-N3 moieties stems from the suitable adsorption energy and favorable reaction energy of the rate-determining step at the Zn active sites. Our findings demonstrate that Zn-N-C SACs hold extraordinary activity toward CTH reactions and thus provide a promising approach to explore the advanced SACs for high-value-added chemicals.

Energizing Co Active Sites via d-Band Center Engineering in CeO2-Co3O4 Heterostructures: Interfacial Charge Transfer Enabling Efficient Nitrate Electrosynthesis.

The electrochemical nitrogen oxidation reaction (NOR) holds significant potential to revolutionize the traditional nitrate synthesis processes. However, the progression in NOR has been notably stymied due to the sluggish kinetics of initial N2 adsorption and activation processes. Herein, the research embarks on the development of a CeO2-Co3O4 heterostructure, strategically engineered to facilitate the electron transfer from CeO2 to Co3O4. This orchestrated transfer operates to amplify the d-band center of the Co active sites, thereby enhancing N2 adsorption and activation dynamics by strengthening the Co─N bond and diminishing the resilience of the N≡N bond. The synthesized CeO2-Co3O4 manifests promising prospects, showcasing a significant HNO3 yield of 37.96 µg h-1 mgcat -1 and an elevated Faradaic efficiency (FE) of 29.30% in a 0.1 m Na2SO4 solution at 1.81 V versus RHE. Further substantiating these findings, an array of in situ methodologies coupled with DFT calculations vividly illustrate the augmented adsorption and activation of N2 on the surface of CeO2-Co3O4 heterostructure, resulting in a substantial reduction in the energy barrier pertinent to the rate-determining step within the NOR pathway. This research carves a promising pathway to amplify N2 adsorption throughout the electrochemical NOR operations and delineates a blueprint for crafting highly efficient NOR electrocatalysts.

Activation of MnO6 Units via an Interfacial Electric Field: Electron Injection into Mn t2g for Rapid and Stable Sodium Ion Storage in CeO2/MnOx.

Manganese-based oxides (MnOx) suffer from sluggish charge diffusion kinetics and poor cycling stability in sodium ion storage. Herein, an interfacial electric field (IEF) in CeO2/MnOx is constructed to obtain high electronic/ionic conductivity and structural stability of MnOx. The as-designed CeO2/MnOx exhibits a remarkable capacity of 397 F g-1 and favorable cyclic stability with 92.13% capacity retention after 10,000 cycles. Soft X-ray absorption spectroscopy and partial density of states results reveal that the electrons are substantially injected into the Mn t2g orbitals driven by the formed IEF. Correspondingly, the MnO6 units in MnOx are effectively activated, endowing the CeO2/MnOx with fast charge transfer kinetics and high sodium ion storage capacity. Moreover, In situRaman verifies a remarkably increased structural stability of CeO2/MnOx, which is attributed to the enhanced Mn─O bond strength and efficiently stabilized MnO6 units. Mechanism studies show that the downshift of Mn 3d-band center dramatically increases the Mn 3d-O 2p orbitals overlap, thus inhibiting the Jahn-Teller (J-T) distortion of MnOx during sodium ion insertion/extraction. This work develops an advanced strategy to achieve both fast and sustainable sodium ion storage in metal oxides-based energy materials.

Mn─O Covalency as a Lever for Na⁺ Intercalation Kinetics: The Role of Oxygen Edge-Sharing Co Octahedral Sites in MnO2.

The strategic enhancement of manganese-oxygen (Mn─O) covalency is a promising approach to improve the intercalation kinetics of sodium ions (Na⁺) in manganese dioxide (MnO2). In this study, an augmenting Mn─O covalency in MnO2 by strategically incorporating cobalt at oxygen edge-sharing Co octahedral sites is focused on. Both experimental results and density functional theory (DFT) calculations reveal an increased electron polarization from oxygen to manganese, surpassing that directed toward cobalt, thereby facilitating enhanced electron transfer and strengthening covalency. The synthesized Co-MnO2 material exhibits outstanding electrochemical performance, demonstrating a superior specific capacitance of 388 F g-1 at 1 A g-1 and maintaining 97.21% capacity retention after 12000 cycles. Additionally, an asymmetric supercapacitor constructed using Co-MnO2 achieved a high energy density of 35 Wh kg-1 at a power density of 1000 W kg-1, underscoring the efficacy of this material in practical applications. This work highlights the critical role of transition metal-oxygen interactions in optimizing electrode materials and introduces a robust approach to enhance the functional properties of manganese oxides, thereby advancing high-performance energy storage technologies.

Electronegative Phosphorus-Integrated Co2+ Active Sites for Enhanced Electrocatalytic Nitrogen Reduction.

In the quest for proficient electrocatalysts for ammonia's electrocatalytic nitrogen reduction, cobalt oxides, endowed with a rich d-electron reservoir, have emerged as frontrunners. Despite the previously evidenced prowess of CoO in this realm, its ammonia yield witnesses a pronounced decline as the reaction unfolds, a phenomenon linked to the electron attrition from its Co2+ active sites during electrocatalytic nitrogen reduction reaction (ENRR). To counteract this vulnerability, we harnessed electron-laden phosphorus (P) elements as dopants, aiming to recalibrate the electronic equilibrium of the pivotal Co active site, thereby bolstering both its catalytic performance and stability. Our empirical endeavors showcased the doped P-CoO's superior credentials: it delivered an impressive ammonia yield of 49.6 and, notably, a Faradaic efficiency (FE) of 9.6% at -0.2 V versus RHE, markedly eclipsing its undoped counterpart. Probing deeper, a suite of ex-situ techniques, complemented by rigorous theoretical evaluations, was deployed. This dual-pronged analysis unequivocally revealed CoO's propensity for an electron-driven valence metamorphosis to Co3+ post-ENRR. In stark contrast, P-CoO, fortified by P doping, exhibits a discernibly augmented ammonia yield. Crucially, P's intrinsic ability to staunch electron leakage from the active locus during ENRR ensures the preservation of the valence state, culminating in enhanced catalytic dynamism and fortitude. This investigation not only illuminates the intricacies of active site electronic modulation in ENRR but also charts a navigational beacon for further enhancements in this domain.

Unlocking Spin Gates of Transition Metal Oxides via Strain Stimuli to Augment Potassium Ion Storage.

Transition metal oxides (TMOs) are key in electrochemical energy storage, offering cost-effectiveness and a broad potential window. However, their full potential is limited by poor understanding of their slow reaction kinetics and stability issues. This study diverges from conventional complex nano-structuring, concentrating instead on spin-related charge transfer and orbital interactions to enhance the reaction dynamics and stability of TMOs during energy storage processes. We successfully reconfigured the orbital degeneracy and spin-dependent electronic occupancy by disrupting the symmetry of magnetic cobalt (Co) sites through straightforward strain stimuli. The key to this approach lies in the unfilled Co 3d shell, which serves as a spin-dependent regulator for carrier transfer and orbital interactions within the reaction. We observed that the opening of these 'spin gates' occurs during a transition from a symmetric low-spin state to an asymmetric high-spin state, resulting in enhanced reaction kinetics and maintained structural stability. Specifically, the spin-rearranged Al-Co3O4 exhibited a specific capacitance of 1371 F g-1, which is 38 % higher than that of unaltered Co3O4. These results not only shed light on the spin effects in magnetic TMOs but also establish a new paradigm for designing electrochemical energy storage materials with improved efficiency.

Spin Symmetry Breaking-Induced Hubbard Gap Near-Closure in N-Coordinated MnO2 for Enhanced Aqueous Zinc-Ion Battery Performance.

Transition metal oxides (TMOs) are promising cathode materials for aqueous zinc ion batteries (ZIBs), however, their performance is hindered by a substantial Hubbard gap, which limits electron transfer and battery cyclability. Addressing this, we introduce a heteroatom coordination approach, using triethanolamine to induce axial N coordination on Mn centers in MnO2, yielding N-coordinated MnO2 (TEAMO). This approach leverages the change of electronegativity disparity between Mn and ligands (O and N) to disrupt spin symmetry and augment spin polarization. This enhancement leads to the closure of the Hubbard gap, primarily driven by the intensified occupancy of the Mn eg orbitals. The resultant TEAMO exhibit a significant increase in storage capacity, reaching 351 mAh g-1 at 0.1 A g-1. Our findings suggest a viable strategy for optimizing the electronic structure of TMO cathodes, enhancing the potential of ZIBs in energy storage technology.

Quantum Spin Exchange Interactions Trigger O p Band Broadening for Enhanced Aqueous Zinc-Ion Battery Performance.

The pressing demand for large-scale energy storage solutions has propelled the development of advanced battery technologies, among which zinc-ion batteries (ZIBs) are prominent due to their resource abundance, high capacity, and safety in aqueous environments. However, the use of manganese oxide cathodes in ZIBs is challenged by their poor electrical conductivity and structural stability, stemming from the intrinsic properties of MnO2 and the destabilizing effects of ion intercalation. To overcome these limitations, our research delves into atomic-level engineering, emphasizing quantum spin exchange interactions (QSEI). These essential for modifying electronic characteristics, can significantly influence material efficiency and functionality. We demonstrate through density functional theory (DFT) calculations that enhanced QSEI in manganese oxides broadens the O p band, narrows the bandgap, and improves both proton adsorption and electron transport. Empirical evidence is provided through the synthesis of Ru-MnO2 nanosheets, which display a marked increase in energy storage capacity, achieving 314.4 mAh g-1 at 0.2 A g-1 and maintaining high capacity after 2000 cycles. Our findings underscore the potential of QSEI to enhance the performance of TMO cathodes in ZIBs, pointing to new avenues for advancing battery technology.

High Flux and Stability of Cationic Intercalation in Transition-Metal Oxides: Unleashing the Potential of Mn t2g Orbital via Enhanced π-Donation.

Transition-metal oxides (TMOs) often struggle with challenges related to low electronic conductivity and unsatisfactory cyclic stability toward cationic intercalation. In this work, we tackle these issues by exploring an innovative strategy: leveraging heightened π-donation to activate the t2g orbital, thereby enhancing both electron/ion conductivity and structural stability of TMOs. We engineered Ni-doped layered manganese dioxide (Ni-MnO2), which is characterized by a distinctive Ni-O-Mn bridging configuration. Remarkably, Ni-MnO2 presents an impressive capacitance of 317 F g-1 and exhibits a robust cyclic stability, maintaining 81.58% of its original capacity even after 20,000 cycles. Mechanism investigations reveal that the incorporation of Ni-O-Mn configurations stimulates a heightened π-donation effect, which is beneficial to the π-type orbital hybridization involving the O 2p and the t2g orbital of Mn, thereby accelerating charge-transfer kinetics and activating the redox capacity of the t2g orbital. Additionally, the charge redistribution from Ni to the t2g orbital of Mn effectively elevates the low-energy orbital level of Mn, thus mitigating the undesirable Jahn-Teller distortion. This results in a subsequent decrease in the electron occupancy of the π*-antibonding orbital, which promotes an overall enhancement in structural stability. Our findings pave the way for an innovative paradigm in the development of fast and stable electrode materials for intercalation energy storage by activating the low orbitals of the TM center from a molecular orbital perspective.

Internal Electric Field Induced by Superexchange Interaction on Mn4+ -O2- -Ni2+ Unit Enables Highly Efficient Hybrid Capacitive Deionization.

Internal electric field (IEF) construction is an innovative strategy to regulate the electronic structure of electrode materials to promote charge transfer processes. Despite the wide use of IEF in various applications, the underlying mechanism of its formation in an asymmetric TM-O-TM unit still remains poorly understood. Herein, the essential principles for the IEF construction at electron occupancy state level and explore its effect on hybrid capacitive deionization (HCDI) performance is systematically investigated. By triggering a charge separation in Ni-MnO2 via superexchange interactions in a coordination structure unit of Mn4+ -O2- -Ni2+ , the formation of an IEF that can enhance charge transfer during the HCDI process is demonstrated. Experimental and theoretical results confirm the electrons transfer from O 2p orbital to TM (Ni2+ and Mn4+ ) eg orbital via superexchange interactions in the basic Mn4+ -O2- -Ni2+ coordination unit. As a result of the charge redistribution, the IEF endows Ni-MnO2 with superior electron and ion transfer property. This work presents a unique material design strategy that activates the electrochemical performance, and provides insights into the formation mechanism of IEF in an asymmetric TM-O-TM unit, which has potential applications in the construction of other innovative materials.

Local Electric Field Induced by Atomic-Level Donor-Acceptor Couple of O Vacancies and Mn Atoms Enables Efficient Hybrid Capacitive Deionization.

Transition metal oxides suffer from slow salt removal rate (SRR) due to inferior ions diffusion ability in hybrid capacitive deionization (HCDI). Local electric field (LEF) can efficiently improve the ions diffusion kinetics in thin electrodes for electrochemical energy storage. Nevertheless, it is still a challenge to facilitate the ions diffusion in bulk electrodes with high loading mass for HCDI. Herein, this work delicately constructs a LEF via engineering atomic-level donor (O vacancies)-acceptor (Mn atoms) couples, which significantly facilitates the ions diffusion and then enables a high-performance HCDI. The LEF boosts an extended accelerated ions diffusion channel at the particle surface and interparticle space, resulting in both remarkably enhanced SRR and salt removal capacity. Convincingly, the theoretical calculations demonstrate that electron-enriched Mn atoms center coupled with an electron-depleted O vacancies center is formed due to the electron back-donation from O vacancies to adjacent Mn centers. The resulted LEF efficiently reduce the ions diffusion energy barrier. This work sheds light on the effect of atomic-level LEF on improving ions diffusion kinetics at high loading mass application and paves the way for the design of transition metal oxides toward high-performance HCDI applications.

Optimizing Electrocatalytic Nitrogen Reduction via Interfacial Electric Field Modulation: Elevating d-Band Center in WS2 -WO3 for Enhanced Intermediate Adsorption.

Electrocatalytic nitrogen reduction reaction (ENRR) has emerged as a promising approach to synthesizing green ammonia under ambient conditions. Tungsten (W) is one of the most effective ENRR catalysts. In this reaction, the protonation of intermediates is the rate-determining step (RDS). Enhancing the adsorption of intermediates is crucial to increase the protonation of intermediates, which can lead to improved catalytic performance. Herein, we constructed a strong interfacial electric field in WS2 -WO3 to elevate the d-band center of W, thereby strengthening the adsorption of intermediates. Experimental results demonstrated that this approach led to a significantly improved ENRR performance. Specifically, WS2 -WO3 exhibited a high NH3 yield of 62.38 µg h-1 mgcat -1 and a promoted faraday efficiency (FE) of 24.24 %. Furthermore, in situ characterizations and theoretical calculations showed that the strong interfacial electric field in WS2 -WO3 upshifted the d-band center of W towards the Fermi level, leading to enhanced adsorption of -NH2 and -NH intermediates on the catalyst surface. This resulted in a significantly promoted reaction rate of the RDS. Overall, our study offers new insights into the relationship between interfacial electric field and d-band center and provides a promising strategy to enhance the intermediates adsorption during the ENRR process.

Shearing Sulfur Edges of VS2 Electrocatalyst Enhances its Nitrogen Reduction Performance.

Electrochemical N2 fixation requires effective electrocatalysts to expedite the nitrogen reduction reaction (NRR) kinetics and suppress the concomitant hydrogen evolution reaction (HER). Although transition metal sulfides have been deemed as efficient NRR electrocatalysts, it remains a great challenge to suppress the serious HER to achieve high Faradaic efficiency (FE). Herein, vanadium disulfide (VS2 ) is deliberately designed by partially shearing its sulfur (S) edges through a simple calcination treatment at 350 °C. The as-prepared VS2 -350 electrocatalyst exhibits a highest NH3 yield of 20.29 µg h-1 mgcat-1 with a promising FE of 3.86%, which is significantly higher than the counterpart of untreated VS2 (VNH3 : 15.92 µg h-1 mgcat-1 , FE: 1.69%). Experimental and computational results reveal that shearing the S edges can substantially inhibit the HER and expose more V atoms as active sites. Meanwhile, the mechanistic analysis shows that the N2 activation at V active sites follows an "acceptance-donation" mechanism, while the N2 conversion to NH3 follows a hybrid 2 pathway at the VS2 -350 electrocatalyst. This work provides a simple strategy of designing high-performance NRR electrocatalysts based on a deep understanding of the atomic sites dependent catalytical activity.

Stabilization of Cu+ via Strong Electronic Interaction for Selective and Stable CO2 Electroreduction.

Copper oxide-based materials effectively electrocatalyze carbon dioxide reduction (CO2 RR). To comprehend their role and achieve high CO2 RR activity, Cu+ in copper oxides must be stabilized. As an electrocatalyst, Cu2 O nanoparticles were decorated with hexagonal boron nitride (h-BN) nanosheets to stabilize Cu+ . The C2 H4 /CO ratio increased 1.62-fold in the CO2 RR with Cu2 O-BN compared to that with Cu2 O. Experimental and theoretical studies confirmed strong electronic interactions between the two components in Cu2 O-BN, which strengthens the Cu-O bonds. Electrophilic h-BN receives partial electron density from Cu2 O, protecting the Cu-O bonds from electron attack during the CO2 RR and stabilizing the Cu+ species during long-term electrolysis. The well-retained Cu+ species enhanced the C2 product selectivity and improved the stability of Cu2 O-BN. This work offers new insight into the metal-valence-state-dependent selectivity of catalysts, enabling the design of advanced catalysts.

Multi-surface catadioptric freeform lens design for ultra-efficient off-axis road illumination.

We propose a novel design methodology to tackle the multi-surface catadioptric freeform lens design for off-axis road illumination applications based on an ideal source. The lens configuration contains an analytic refractive entrance surface, an analytic total internal reflective (TIR) surface and two freeform exit surfaces. A curl-free energy equipartition is established between the source and target plane and applied to implement the composite ray mapping mechanism. Furthermore, the analytic TIR surface and refractive entrance surface are optimized for the minimal Fresnel losses and surface error based on Genetic algorithm (GA). The results show a significant improvement on illuminance uniformity and ultra-high transfer efficiency compared to the design employed our proposed method in [Zhu et al., Opt. Express 26, A54-A65 (2018)].

Modulating the d-Band Center of Palladium via Ethylene Glycol Modification: Accelerating Had Desorption for Enhanced Formate Electrooxidation.

This study addresses the critical challenge in alkaline direct formate fuel cells (DFFCs) of slow formate oxidation reaction (FOR) kinetics as a result of strong hydrogen intermediate (Had) adsorption on Pd catalysts. We developed WO3-supported Pd nanoparticles (EG-Pd/WO3) via an organic reduction method using ethylene glycol (EG), aiming to modulate the d-band center of Pd and alter Had adsorption dynamics. Cyclic voltammetry demonstrated significantly improved Had desorption kinetics in EG-Pd/WO3 catalysts. Density functional theory (DFT) calculations revealed that the presence of EG reduces the d-band center of Pd, leading to weaker Pd-H bonds and enhanced Had desorption during the FOR. This research provides a new approach to optimize catalyst efficiency in DFFCs, highlighting the potential for more effective and sustainable energy solutions through advanced material engineering.

Inducing weak and negative Jahn-Teller distortions to alleviate structural deformations for stable sodium storage.

In the quest for efficient supercapacitor materials, manganese-based layered oxide cathodes stand out for their cost-effectiveness and high theoretical capacity. However, their progress is hindered by the Jahn-Teller (J-T) distortion due to the unavoidable Mn4+ to Mn3+ reduction during ion storage processes. Our study addresses this challenge by stabilizing the K0.5MnO2 cathode through strategic Mg2+ substitution. This substitution leads to an altered Mn3+ electronic configuration, effectively mitigating the strong J-T distortion during ion storage processes. We provide a comprehensive analysis combining experimental evidence and theoretical insights, highlighting the emergence of the weak and negative J-T effects with reduced structural deformation during electrochemical cycling. Our findings reveal that the K0.5Mn0.85Mg0.15O2 cathode exhibits remarkable durability, retaining 96.0% of initial capacitance after 8000 cycles. This improvement is attributed to the specific electronic configurations of Mn3+ ions, which play a crucial role in minimizing volumetric changes and counteracting structural deformation typically induced by the strong J-T distortion. Our study not only advances the understanding of managing J-T distortion in manganese-based cathodes but also opens new avenues for designing high-stability supercapacitors and other energy storage devices by tailoring electrode materials based on their electronic configurations.

Cu-Modified Palladium Catalysts: Boosting Formate Electrooxidation via Interfacially OHad-Driven Had Removal.

Direct formate fuel cells have gained traction due to their eco-friendly credentials and inherent safety. However, their potential is hampered by the kinetic challenges of the formate oxidation reaction (FOR) on Pd-based catalysts, chiefly due to the unfavorable adsorption of hydrogen species (Had). These species clog the active sites, hindering efficient catalysis. Here, we introduce a straightforward strategy to remedy this bottleneck by incorporating Pd with Cu to expedite the removal of Pd-Had in alkaline media. Notably, Cu plays a pivotal role in bolstering the concentration of hydroxyl adsorbates (OHad) on the surface of catalyst. These OHad species can react with Had, effectively unblocking the active sites for FOR. The as-synthesized catalyst of PdCu/C exhibits a superior FOR performance, boasting a remarkable mass activity of 3.62 A mg-1. Through CO-stripping voltammetry, we discern that the presence of Cu in Pd markedly speeds up the formation of adsorbed hydroxyl species (OHad) at diminished potentials. This, in turn, aids the oxidative removal of Pd-Had, leveraging a synergistic mechanism during FOR. Density functional theory computations further reveal intensified interactions between adsorbed oxygen species and intermediates, underscoring that the Cu-Pd interface exhibits greater oxyphilicity compared to pristine Pd. In this study, we present both experimental and theoretical corroborations, unequivocally highlighting that the integrated copper species markedly amplify the generation of OHad, ensuring efficient removal of Had. This work paves the way, shedding light on the strategic design of high-performing FOR catalysts.

Interfacial Push-Pull Dynamics Enable Rapid Had Desorption for Enhanced Formate Electrooxidation.

The electrocatalytic conversion of formate in alkaline solutions is of paramount significance in the realm of fuel cell applications. Nonetheless, the adsorptive affinity of adsorbed hydrogen (Had) on the catalyst surface has traditionally impeded the catalytic efficiency of formate in such alkaline environments. To circumvent this challenge, our approach introduces an interfacial push-pull effect on the catalyst surface. This mechanism involves two primary actions: First, the anchoring of palladium (Pd) nanoparticles on a phosphorus-doped TiO2 substrate (Pd/TiO2-P) promotes the formation of electron-rich Pd with a downshifted d band center, thereby "pushing" the desorption of Had from the Pd active sites. Second, the TiO2-P support diminishes the energy barrier for Had transfer from the Pd sites to the support itself, "pulling" Had to effectively relocate from the Pd active sites to the support. The resultant Pd/TiO2-P catalyst showcases a remarkable mass activity of 4.38 A mgPd-1 and outperforms the Pd/TiO2 catalyst (2.39 A mgPd-1) by a factor of 1.83. This advancement not only surmounts a critical barrier in catalysis but also delineates a scalable pathway to bolster the efficacy of Pd-based catalysts in alkaline media.

Built-in Electric Field-Induced Work Function Reduction in C-Co3O4 for Efficient Electrochemical Nitrogen Reduction.

Co3O4 is a highly selective catalyst for the electrochemical conversion of N2 to NH3. However, the large work function (WF) of Co3O4 leads to unsatisfactory activity. To address this issue, a strong built-in electric field (BIEF) was constructed in Co3O4 by doping C atoms (C-Co3O4) to reduce the WF for improving the electrocatalytic performance. C-Co3O4 exhibited a remarkable NH3 yield of 38.5 µg h-1 mgcat-1 and a promoted FE of 15.1% at -0.3 V vs RHE, which were 2.2 and 1.9 times higher than those of pure Co3O4, respectively. Kelvin probe force microscopy (KPFM), zeta potential, and ultraviolet photoelectron spectrometry (UPS) confirmed the formation of strong BIEF and WF reduction in C-Co3O4. Additionally, in situ Raman measurements and density functional theory (DFT) calculations revealed the relationship between BIEF and WF and provided insights into the reaction mechanism. Our work offers valuable guidance for the design and development of more efficient nitrogen reduction catalysts.