Hydrogen sulfide (H2S) serves as an exhaled-breath biomarker for conditions such as halitosis and asthma. To address fundamental inefficiencies in charge collection and transport within disordered conductive metal-organic frameworks films, a Cu-HHTP/NUS-8 MOF-on-MOF structure is constructed. The resulting composite features a uniformly oriented and open nanoarchitecture, which facilitates efficient gas diffusion and exposes interior active sites. The Cu-HHTP/NUS-8 chemiresistive sensor shows a 63.4% response to 5 ppm H2S at room temperature, with a theoretical limit of detection (LOD) of similar to 23 ppb. It retains a strong response under high humidity and only 5.4% decay over 31 days. Integrating it as a floating-gate in a carbon nanotube field-effect transistor (CNTFET) further amplifies the detection signal. At V-gs = 2.0 V, the device exhibits a 70.5% response to 0.1 ppm H2S, with a theoretical LOD of similar to 0.71 ppb. This is similar to 30.2-fold better than the chemiresistive mode, with sensitivity rising from 20.74%/ppm to 625.93%/ppm. These results prove interfacial-templated MOF-on-MOF boosts molecular accessibility and charge efficiency, offering a scalable route to high-performance room-temperature H2S sensors.

The electrochemical ethanol oxidation reaction (EOR) in acid offers a promising route for co-producing hydrogen and value-added chemicals, but suffers from severe Pt catalyst poisoning and poor stability. Herein, we report the synthesis of ultrathin PtNi nanowires (NWs) with abundant step defects for efficient and stable EOR. The PtNi NWs/C catalyst exhibits high mass activity (1.50 A mgPt-1@0.7 V vs. RHE), Faradaic efficiency (80% to acetic acid), and stability compared to the Pt NWs/C and Pt NPs/C counterparts. It has been demonstrated that the ultrathin NW structure endowed the PtNi NWs/C with high electrochemical active surface area and abundant step sites, while the incorporation of Ni facilitates the removal of poisoning CO and accelerates the EOR kinetics on Pt via the in-situ formation of Ni(III), leading to the superior performance. A practical electrolyzer using the PtNi NW as the anodic catalyst achieves 132 mA cm-2 at 0.8 V and sustains operation for 100 h.

Solar-driven interfacial evaporation (SDIE) is a low-energy and environmentally friendly technology for clean-water production. However, when applied to complex waters, volatile organic compounds (VOCs) can readily enter the condensate. In this study, a sequential strategy involving carbonization followed by composite fabrication was used to construct a CuO@Fe2O3@CC-SA (CFCC-SA) bimetallic oxide aerogel evaporator with both mechanical stability and flexibility for efficient water evaporation and VOC degradation. Synergistic interactions between Fe and Cu enhanced both the photothermal conversion efficiency and Fenton-like catalytic activity of the material. Meanwhile, the porous aerogel network provided excellent hydrophilicity and rapid water transport, thereby promoting efficient evaporation. Under 1.0 kW m–2 irradiation, the CFCC-SA evaporator exhibited an evaporation rate of 2.06 kg·m–2·h–1, corresponding to an approximately 20% increase relative to the monometallic CuO@CC-SA evaporator. For phenol, CFCC-SA achieved removal efficiencies of 98.4% in the condensate and 63.8% in the raffinate. Furthermore, CFCC-SA maintained high phenol removal performance over a broad pH range and under highly saline conditions (20 wt% NaCl). Overall, by integrating efficient water transport with synergistic bimetallic catalysis, the CFCC-SA evaporator offers a promising strategy for designing SDIE systems that simultaneously enable high-rate water evaporation and VOC removal.

Machine learning (ML) is transforming the discovery of electrocatalysts for the carbon-neutral energy transition by overcoming the limitations of trial-and-error experimentation and costly quantum simulations. This review summarizes recent advances in data-driven electrocatalysis, focusing on two emerging paradigm shifts: autonomous literature mining assisted by large language models (LLMs) and materials representation via graph neural networks (GNNs). We first trace the evolution from manual data curation to LLM-assisted mining, which accelerates database construction by orders of magnitude; then, the shift from handcrafted descriptors to GNNs, which expands the computational screening space from thousands to millions of candidates. Subsequently, we discuss key algorithms-including active learning and symbolic regression-and their applications in the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and carbon dioxide reduction reaction (CO2RR), illustrating how they help identify non-intuitive descriptors that rationalize activity trends. We also highlight how these descriptor-based predictions guide the discovery of specific catalyst motifs or reaction pathways that can circumvent or break complex scaling relations inherent in multi-electron transfer processes. We then critically discuss challenges related to data heterogeneity, model interpretability, and the synthesis-performance gap, before offering a perspective on integrating physics-informed ML and autonomous self-driving laboratories to accelerate the rational design of next-generation electrocatalysts.

One of the most promising paths for the scalable use of photocatalytic nanomaterials is their immobilization onto proper matrixes to enable catalyst reuse and separation. In this work, photocatalytic membranes (PZISNi-x) were prepared employing polyacrylonitrile and polyethylene glycol (PAN-PEG) precursors via non-solvent induced phase inversion, incorporating a pre-synthesized 2D-2D ZnIn2S4 (ZIS)/Ni-MOF-74 heterojunction as a casting scaffold to enable visible-light-driven hydrogen production. The effect of photocatalyst loading (x = 0, 2, 5, 10, 15 and 20%) on membrane morphology, compositional, optical, electrochemical and photocatalytic properties was systematically investigated. The incorporated Ni-rich ZIS (ZIS@Ni) photocatalysts were homogenously immobilized within the membrane, while structural, surface and compositional analyses confirmed an ultra-low and controlled incorporation of active Ni sites in the PZISNi-x samples. The hydrogen evolution rate tops for the PZISNi-15 sample (0.77 +/- 0.08 mmol g- 1 h- 1), representing a sixfold enhancement compared to the pure ZIS loaded membrane counterpart (PZIS-15). The PZISNi-15 membrane also shows an apparent quantum efficiency (AQE) of 2.1 +/- 0.6% at 420 nm and excellent stability over repeated cycles. Optical and electrochemical analysis shows improved charge separation and favorable band alignment induced by Ni incorporation. These results demonstrate that PAN-PEG supported ZIS@Ni membranes constitute a robust and scalable platform for immobilized photocatalytic hydrogen generation.

The key to advancing Zn-air batteries (ZABs) and flexible Zn-air batteries (FZABs) lies in creating electrocatalysts with flexibility, porosity, high efficiency, and stability. Herein, Cu/Fe-N@PCFs is prepared by electrospinning and pyrolysis. Fe-ZIF-8 serves as a carbon and nitrogen source dispersing Fe sites, and promotes the formation of microporous structures during pyrolysis together with NaCl. Cu species are introduced onto the surface of Fe-N@PCFs to interact with Fe-Nx sites and alleviate the Fenton-like effect, synergistically enhancing the bifunctional oxygen electrocatalytic performance toward oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The fibrous structure improves the peak power density of ZAB and FZAB. The Cu/Fe-N@PCFs exhibits an ORR half-wave potential (E1/2) of 0.865 V (vs. 0.838 V for Pt/C) and an OER overpotential of 370 mV (vs. 305 mV for RuO2) at 10 mA cm−2. The ZAB achieves a peak power density of 278.2 mW cm−2 (vs. 145.5 mW cm−2 for Pt/C + RuO2) and durability of 190 h. The self-supporting Cu/Fe-N@PCFs is assembled as FZAB, delivering a peak power density of 82.4 mW cm−2 (vs. 16.4 mW cm−2 for Pt/C + RuO2) and durability of 17 h. This study provides significant perspectives on constructing flexible catalysts, potentially advancing the development of ZABs and FZABs.

Ethylene glycol oxidation reaction (EOR) holds great significance for biomass fuel cell applications and highvalue chemical synthesis, yet it is plagued by sluggish reaction kinetics, poor anti-poisoning capability, and inefficient C-C bond cleavage. This work reports a Eu(OH)3-Ni(OH)2 heterostructure which is in-situ grown on nickel foam via a facile two-step hydrothermal method, aiming to explore the electronic modulation of rare-earth 4f orbitals on transition metal hydroxides. Structural and morphological characterizations verify the successful fabrication of an intimate heterostructure. Electronic structure analysis and density functional theory (DFT) calculations reveal a distinctive ternary orbital coupling system of Ni 3d-O 2p-Eu 4f. In this system, O 2p orbitals serve as a bridge for directional electron transfer from Eu to Ni sites, optimizing Ni's d-band center, balances the adsorption and desorption behaviors of reaction intermediates, and lowers the energy barriers of key reaction steps, and reducing key step energy barriers. The Eu(OH)3-Ni(OH)2-NF electrode delivers outstanding EOR performance. It achieves 98.3% EG conversion and 96.9% formate selectivity. In-situ spectra and NMR confirm the stepwise pathway. This work provides a universal orbital coupling strategy for designing rare-earth/ transition metal electrocatalysts.

Green electrochemical energy storage is essential for carbon neutrality, and alkaline zinc batteries offer a compelling solution due to their inherent safety, low cost, and high energy density. However, their performance is limited by parasitic reactions, including corrosion, gas evolution, and slow Zn/ZnO conversion kinetics stemming from inefficient dissociation of the tetrahydroxozincate [Zn(OH) 4 2− ] intermediate. We address this by designing a series of cobalt porphyrins (Co‐4N, Co‐3N‐O, Co‐3N‐S) that modulate the metal center's charge density for accelerating Zn(OH) 4 2 − decomposition, and control Zn 2 + transport through the carboxyl‐functionalized peripheries. The Co‐3N‐O‐modified electrolyte achieves exceptional stability, maintaining stable cycle for over 80,000 s at 5 mA cm − 2 , which is more than four times longer than the <20,000 s achieved by the conventional KOH + ZnO electrolyte. In Zn||Ni batteries, this molecularly engineered electrolyte enables 110 stable cycles at 1 mA cm −2 , significantly outperforming the unmodified system, which sustained only 20 cycles. These findings elucidate a structure‐kinetics relationship for zincate regulation and demonstrate how customized molecular asymmetry can overcome persistent challenges in aqueous battery chemistry, offering a pathway to high‐performance, durable energy storage systems.

Single-atom catalysts (SACs) are promising for hydrogen evolution due to their maximal atomic utilization and discrete energy levels. Modulating metal-support interactions is key to tailoring their activity and stability, yet achieving precise control and mechanistic insight remains challenging and controversial. Here, we construct a rhodium single-atom catalyst model system, with Rh atoms anchored on a series of MoSxSe2-x supports (RhSA-MoSxSe2-x, 0 ≤ x ≤ 2), enabling gradient modulation of metal-support frontier orbital interactions through systematic tuning the anion composition. The elevated lowest unoccupied molecular orbital (LUMO) of MoSxSe2-x support narrows the energy gap with the highest occupied molecular orbital (HOMO) of Rh atoms, strengthening metal-support orbital hybridization to enhance stability and further amending the LUMO of Rh atoms to optimize both the hydroxide and hydrogen adsorption for high activity. The apex RhSA-MoSSe catalyst, with optimal HOMO-LUMO hybridization, achieves favorable hydrogen evolution reaction activity and stability simultaneously. This work offers fundamental insights into the metal-support frontier orbital interaction in SACs and establishes a rational design framework for high activity and stability electrocatalysis.

ABSTRACT Hydrogen sulfide (H 2 S) serves as an exhaled‐breath biomarker for conditions such as halitosis and asthma. To address fundamental inefficiencies in charge collection and transport within disordered conductive metal–organic frameworks films, a Cu‐HHTP/NUS‐8 MOF‐on‐MOF structure is constructed. The resulting composite features a uniformly oriented and open nanoarchitecture, which facilitates efficient gas diffusion and exposes interior active sites. The Cu‐HHTP/NUS‐8 chemiresistive sensor shows a 63.4% response to 5 ppm H 2 S at room temperature, with a theoretical limit of detection (LOD) of ∼23 ppb. It retains a strong response under high humidity and only 5.4% decay over 31 days. Integrating it as a floating‐gate in a carbon nanotube field‐effect transistor (CNTFET) further amplifies the detection signal. At V gs = 2.0 V, the device exhibits a 70.5% response to 0.1 ppm H 2 S, with a theoretical LOD of ∼0.71 ppb. This is ∼30.2‐fold better than the chemiresistive mode, with sensitivity rising from 20.74%/ppm to 625.93%/ppm. These results prove interfacial‐templated MOF‐on‐MOF boosts molecular accessibility and charge efficiency, offering a scalable route to high‐performance room‐temperature H 2 S sensors.

Metal-free carbon materials are promising catalysts for the electrochemical CO2 reduction reaction (CO2RR). However, the principles for regulating carbon materials still require further discussion. In this context, p-block elements with varying electronegativity may offer extensive opportunities for modulating the electronic properties of the active sites. Herein, density functional theory (DFT) calculations are performed on carbon materials functionalized with p-block elements to reveal their key role in the CO2RR. We systematically screened 14 graphene nanoribbon edge models functionalized with different p-block functional groups (Edge-X/C). The results indicate that the electronegativity of the functional groups serves as a key parameter, which effectively tunes both the p-band center and the surface work function of the carbon atoms. Furthermore, a volcano-shaped relationship was observed between the p-band center and catalytic activity. This indicates that moderate orbital energy levels suppress excessive electron back-donation and promote CO desorption, which are beneficial for the CO2RR. Edge-AsH2/C exhibits the lowest theoretical limiting potential due to the moderate p-band center of its active sites. These insights provide a robust framework for the rational design of high-performance, metal-free electrocatalysts.

Electrochemical Nitrate Reduction (NO 3 − RR) is a promising green process for producing ammonia and treating waste water. The nitrate‐to‐ammonia reduction involves multi‐step electron/proton‐transfer processes, where the NO 3 − →NO 2 − step may serve as the rate‐determining step, posing a critical bottleneck for efficient NH 3 synthesis. In this paper, the emulsion hydrothermal method is used to synthesize spherical and nanoflower‐like CuO/CuCo 2 O 4 catalysts with small particle stacking. Among them, CuCo 2 O 4 perfectly inherits the advantages of CuO and Co 3 O 4 , and successfully connects the two‐step reactions of NO 3 − →NO 2 − and NO 2 − →NH 3 in series. The CuO formed by excess copper doping is reduced to monomeric copper during electrolysis. Cu is able to synergize with CuCo 2 O 4 to break through the bottleneck of the rate‐limiting step of NO 3 − →NO 2 − , exhibiting almost the same ammonia production efficiency in both NO 3 − RR and nitrite reduction reaction (NO 2 − RR). The NH 3 yield of Cu/CuCo 2 O 4 at −0.70 V (vs RHE) reached a maximum of 24.58 mg h −1 mg cat −1 under neutral electrolyte conditions and exhibited 100% Faraday efficiency for NH 3 . Under the same conditions (where the reaction substrate is NO 2 − ), Cu/CuCo 2 O 4 reached an NH 3 yield of 24.34 mg h −1 mg cat −1 in NO 2 − RR.

Spin state of active sites is one of the most influencing factors for the catalytic performance of electrocatalysts. To date, most modulations are conducted on non-tetrahedrally coordinated metal sites, while tetrahedron-coordinated single-atom catalysts (TCSACs) have not been investigated yet. This article presents a correlation between the spin state of TCSACs and their activities toward CO2 electroreduction. TCSACs are made using ZnO as the substrate. The spin states of metal sites of TCSACs modulate the interactions between the catalyst and adsorbed intermediates. A volcano relationship is found between the transition metal (TM) magnetic moments and the limiting potential (UL) of the CO2 reduction reaction. Spin-state analysis indicates that the intermediate spin state of TMs is more favorable for the adsorption and conversion of CO2. Optimal interaction between the TM-t2 orbitals of the intermediate spin and the adsorbed molecule-pz orbitals significantly improves the catalytic activity of the TCSACs. As a result, Fe-TCSAC achieves a high FECO of 91.6% at -0.9 V vs RHE. These results provide a theoretical basis and guidelines for the spin-state effects of tetrahedron-coordinated single-atom catalysts.

The development of oxygen evolution reaction (OER) catalysts based on non-noble metals that have high catalytic activity and long-term stability is crucial for the use of an anion exchange membrane water electrolyzer (AEMWE). Here, we report a three-layer composite OER catalyst, NiFe-LDH/CoPi/NF, with the cobalt phosphate (CoPi) interlayer in the middle of nickel foam and a NiFe-LDH nanosheet array. The CoPi interlayer significantly improves the OER catalytic activity as well as the stability. The overpotential required for NiFe-LDH/CoPi/NF to achieve an OER current density of 1000 mA·cm-2 is only 277 mV, and the performance has almost no attenuation for 1000 h of continuous working at 1000 mA·cm-2. The AEMWE using NiFe-LDH/CoPi/NF as an anode reached a current density of 1 A·cm-2 at the cell voltage of only 1.709 V, and it stably operated up to 1200 h. It is found that the CoPi interlayer modulated the morphology of the NiFe-LDH nanosheet arrays and also tuned the electronic structure of the NiFe-LDH. The Ni in NiFe-LDH/CoPi/NF shows a higher valence state, thereby promoting its activity, and also shows a low dissolution rate, thereby promoting its stability.

Improving the strength and toughness of fractured coal bodies during pressure relief in impact rock roadway drilling, a reinforced and toughened grouting material (PCGN) was developed using cement (P), coal gangue (CG), graphene oxide (GO), and nanosilica (N-S) as raw materials. The stability and mechanical properties of PCGN were investigated through flowability experiments, water separation rate experiments, and uniaxial compressive strength (6c) and tensile strength (6t) experiments. The phase, microstructure, and pore characteristics of PCGN were analyzed via X-ray diffraction (XRD) and scanning electron microscopy (SEM). Finally, the brittleness coefficient (BE) and static toughness (eta) were used to evaluate the toughness of PCGN, and based on acoustic emission (AE) and digital speckle pattern (DIC) monitoring data, the fracture mechanism and crack propagation law of PCGN were studied. The results revealed the following. 1) The 6c and 6t of PCGN first increased but then decreased with increasing GO content, reaching their maximum values at 0.06 %. GO promoted the cement hydration reaction and reduced the porosity of PCGN. 2) CG and N-S weakened the brittleness of the PCGN, and the BE first decreased and then increased with increasing CG and N-S mass fractions. 3) The fracture mechanism of PCGN varied greatly at different levels of brittleness. As the BE decreases, the fracture mode of PCGN gradually evolves from large-scale multicrack splitting failure to small-scale uniform single crack shear failure.

Direct electrolysis of pH-neutral seawater for hydrogen generation is a promising method for storing renewable energy. However, the oxygen evolution reaction (OER) faces a selectivity challenge, competing with chlorine evolution and confronting severe corrosion issues of the electrode. Here, we have synthesized ultrathin, polycrystalline, porous Co3O4 nanosheets with Pd single atoms (PdSA-Co3O4) for efficient and stable pH-neutral seawater decomposition. The octahedral Pd-O-Co active unit, generated by the synergistic coordination of the Pd single atom strong proton adsorption (SPA) material with Co3O4 nanosheets, resulted in PdSA-Co3O4 have activities 3, 5, and 31 times higher than Co3O4, IrO2, and commercial Co3O4, respectively. It also remained stable in pH-neutral seawater for 80 h. Operando in situ Raman spectroscopy combined with density functional theory calculations showed that synergistic interactions between the strong proton adsorption of Pd single atoms and the active site Co enhanced the adsorption of intermediates and significantly reduced the free energy of adsorption at the rate-determining step (O*-+OOH*). The Pd-O-Co active units inhibited the transformation of the dynamic structure of the Co3O4 substrate and reduced the corrosive effect of Cl ions during the OER process.

Seawater batteries (SWBs) are promising energy conversion systems that directly utilize seawater as an electrolyte for converting chemical energy into electricity. The oxygen reduction reaction (ORR) occurs by consuming dissolved oxygen on the cathode electrocatalysts for discharging. However, chloride ions (Cl-) poison the surface catalytic sites of electrocatalysts, and the low dissolved oxygen concentration critically limits the ORR reaction kinetics, reducing the discharging power density and working life. In this work, we designed and synthesized the Fe/Se-NC electrocatalyst using a facile solution chemical process. Theoretical calculation and experimental results suggest that the incorporation of Se in Fe/Se-NC can significantly enhance the adsorption energy of Cl- on one side of the Fe site (designated as Fe/Se-NC-Cl) and result in the enhanced oxygenophilic property of Fe/Se-NC on another side of the Fe site. This simultaneously enhances Cl-corrosion resistance and ORR activity. The Fe/Se-NC-Cl electrocatalysts display outstanding ORR onset and half-wave potentials of 0.88 and 0.75 V, respectively, which rank at the top among ORR electrocatalysts in natural seawater electrolyte. The SWBs using Fe/Se-NC-Cl as cathodes show a high peak power density of 94 mW cm -2, stability of more than 450 h, and discharge capacity of 583 Wh kg -1 at a current density of 5 mA cm -2 in natural seawater electrolyte. The developed SWB package can efficiently power household appliances with a rated power of up to 50 W.

Substituting the kinetically sluggish oxygen evolution reaction with the thermodynamically favorable benzyl alcohol oxidation reaction is a compelling strategy for producing high-value chemicals and hydrogen. Herein, phosphorus (P)-doped hollow spherical shell structure NiS2 with abundant sulfur (S) vacancy, denoted as Svac-P-NiS2, was synthesized and investigated as a bifunctional electrocatalyst for benzyl alcohol (BA) oxidation and hydrogen evolution reaction (HER). Two important processes occured during P doping; (1) the formation of high valence nickel (Ni3+), wherein the electrons in the Ni eg orbit flowed to the foreign P and (2) the Ni-S antibonding orbit became more susceptible to accepting electrons and facilitating the formation of S vacancy. The above results were confirmed using X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and crystal orbital Hamilton population (COHP) analysis. High-valence Ni, as a high-energy catalytic active site, lowered the energy barrier of the reaction rate-determining step and accelerated the reaction kinetics. Meanwhile, the S vacancy contributed to the activation of C-H bonds in benzyl alcohol, as demonstrated by differential charge density calculations and quantified by pCOHP calculations. Owing to these advantages, the dopant and vacancy exhibited indispensable synergistic effects in the electrocatalytic process, which greatly promoted the electrocatalytic performance of Svac-P-NiS2. This work provides insights into the formation mechanisms of vacancies in doped materials and elucidates the nature of the improved catalyst performance.

Seawater electrocatalysis is highly desired for a variety of energy storage and conversion systems, such as water splitting and metal fuel cells that directly using seawater as electrolyte. However, the adsorption of chloride ions (Cl-) on active sites of cathodes would worsen the oxygen reduction reaction (ORR) activity and stability, thus lowering the battery performance. In this work, we firstly designed an electrocatalyst model, in which the Co atomic clusters were closely surrounded by satellite Co single atoms on N-doped carbon substrates, designated as Co-ACSAs. The theoretical calculation results suggested that the Co clusters possess stronger Cl- binding energy and acted as pre-adsorption group for Cl-, thus fully exposed Co single atoms as ORR active sites with stronger O2 adsorption energy to promote the oxygen reduction reaction process. Then, we developed an ultrafast high temperature shock strategy to synthesize the Co-ACSAs by controlling the N concentration in carbon substrates. Benefiting from the moderate interacting distance between Co clusters and satellite Co single atoms in Co-ACSAs, the electronic structure of Co clusters and Co single atoms was optimized through the modulation of the interconnected hexatomic ring. As a result, Co-ACSAs exhibit superior ORR activity and durability with on-set and half-wave potentials of 0.885 V and 0.782 V, respectively, and continuously catalyzing for 485 h in seawater electrolyte. The Co-ACSAs-based seawater battery exhibits a discharge voltage of 1.41 V at 5 mA cm-2 and realized stable energy supply for more than 390 h.

Electrochemical synthesis of ammonia through nitrogen reduction reaction (NRR) is cost-effective and energy-effective compared to the conventional Haber-Bosch process. However, the slow activation kinetics of N2 hindered the development of active and selective catalysts. In this work, we showed that transition metal (TM) single atoms anchored on monolayer molybdenum disulfide (MoS2) with 1T phase could promote its phase transition to 1T' due to broken surface symmetry induced by TM atoms. By combining the high-throughput screening with DFT calculations in transition metals, two TM elements (V, Ti) anchored on 1T'-MoS2 were proved to be promising candidates in N2 fixation. The V and Ti single-atom catalyst exhibits low Gibbs free energy barrier, and Ti single-atom catalyst shows the highest selectivity towards NH3. Moreover, the stability of single-atom TM@1T'-MoS2 was measured with the ab initio molecular dynamics (AIMD) simulations. The density of states (DOS) and surface charge analysis were conducted to reveal the origin of improved activities. Our results pave the way to design more innovative single-atom catalysts for high-performance electrocatalytic NRR.