Designing efficient and stable oxygen evolution reaction (OER) electrocatalysts for anion exchange membrane water electrolysis (AEMWE) systems is critical for sustainable energy conversion. Here, we demonstrate a strain engineering strategy through hydrothermal impregnation to anchor W single atoms on MnO2 nanofibers, effectively modulating their electronic structure. The introduced tensile strain weakens the metal-oxygen bond strength, triggering a transition of the OER mechanism from the adsorbate evolution mechanism to the lattice oxygen-mediated mechanism-oxygen vacancy site mechanism (LOM-OVSM). The optimized W-2.06%-MnO2 exhibits superior OER performance with an overpotential of 230 mV at 10 mA cm(-2). When applied in an AEMWE cell, it requires 1.77 V to drive 1 A cm(-2) and demonstrates continuous operation for over 450 h. This study provides fundamental insights into strain-induced modulation of reaction pathways and offers a practical strategy for designing advanced electrocatalysts toward scalable green hydrogen production.

Intermittent renewable energy-driven seawater hydrogen production can alleviate freshwater resource pressure and is of great significance in future energy systems. However, the localized microenvironment changes at the cathode and the strong interactions between other impurities and the electrolyzer lead to performance degradation and reduced equipment lifespan. Here, we report an alkaline seawater cathode catalyst for hydrogen production in an anion exchange membrane water electrolyzer (AEMWE). This catalyst can dynamically adjust the local reaction environment on the cathode surface. Through the reversible changes in the oxidation state of Pt in high-entropy intermetallic compounds, a Brønsted acid-like environment is formed near the reaction interface, inhibiting the formation of precipitates. In situ characterization confirmed that this Brønsted acid-like environment can promote hydrogen production from alkaline seawater. Using alkaline seawater electrolysis, AEMWE operated stably for over 2000 h at an industrial-grade current density of 1.0 A cm-2 (1.74 V).

Direct seawater electrolysis is a promising strategy for sustainable hydrogen production, yet it is severely hindered by the sluggish kinetics of the oxygen evolution reaction (OER) and aggressive chloride (Cl⁻) corrosion at the anode. To address these bottlenecks, we propose a synergistic "inner-doping and outer-coating" strategy to construct oxygen vacancy-rich CeO2-x-encapsulated, Nb-doped NiFe-LDH core-shell heterostructure arrays on nickel foam (CeO2-x@NiFeNb-LDH/NF). Mechanistic investigations reveal that the internal Nb doping optimizes the electronic structure of the NiFe-LDH laminae, accelerating intrinsic charge transfer. Simultaneously, the outer CeO2-x shell not only boosts catalytic activity via strong metal-support interactions but also serves as a robust physical and chemical dual-barrier to efficiently repel Cl⁻ penetration. Consequently, the as-synthesized catalyst exhibits outstanding bifunctional activity in alkaline media, requiring ultra-low overpotentials of only 125.6 mV for OER and 93 mV for the hydrogen evolution reaction (HER) at 10 mA cm-2. When deployed as a bifunctional electrode for overall water splitting, the system requires a low cell voltage of 1.56 V to reach an industrial-level current density of 100 mA cm-2 in simulated alkaline seawater, delivering stable operation for over 120 hours without noticeable degradation. This work demonstrates a highly effective paradigm to break the activity-stability trade-off of non-noble metal catalysts for practical seawater electrolysis.

ABSTRACT The rational construction of a reverse hydrogen spillover channel within the catalyst effectively accelerates hydrogen evolution reaction (HER) kinetics, whereas the driving forces and mechanisms that control hydrogen surface migration remain insufficiently investigated. Therefore, we constructed a strongly coupled RuO x ‐Mo 2 C cluster‐cluster heterostructure catalyst to effectively induce the reverse hydrogen spillover effect. Owing to the high‐density accessible active sites and efficient mass transport pathways provided by the strongly coupled cluster structure, hydrogen can migrate directionally and rapidly from Mo 2 C sites to RuO x sites via the reverse hydrogen spillover effect. This well‐defined interfacial coupling and functional partitioning substantially reduce the integrated energy barrier for water dissociation, H * transport, and H‐H coupling, leading to drastically accelerated HER kinetics and excellent electrocatalytic activity toward hydrogen evolution. It exhibits an overpotential of only 15 mV at 10 mA cm −2 . Moreover, the catalyst maintains stable performance for up to 1000 h under continuous electrolysis without significant degradation, demonstrating outstanding structural and catalytic stability. Furthermore, an anion exchange membrane water electrolyzer with RuO x ‐Mo 2 C as the cathode delivers superior catalytic activity, exhibiting a cell voltage of 1.76 V at 1.0 A cm −2 and long‐term stability over 1500 h, holding great promise for industrial high‐current applications.

Photocatalytic hydrogen production from water using solar energy represents a promising pathway for energy-intensive societies to overcome sustainability bottlenecks. However, the design and controllable synthesis of photocatalytic materials with high performance, high stability, and environmental compatibility remains challenging. The localized electronic structures and strongly bound Frenkel excitons in metal-free graphitic carbon nitride (g-C3N4) result in poor photocatalytic performance. To address these limitations, this work employs Density Functional Theory (DFT) calculations to guide the design and synthesis of g-C3N4 photocatalytic materials (EHTD-CN). Specifically, the integration of spatially separated electron-trapping and hole-trapping domains (ETD and HTD) alters the distribution of electron density. This creates a robust built-in electric field (BIEF) within symmetry-breaking conjugated frameworks, reducing the exciton binding energy and promoting photoexciton dissociation and subsequent migration to predetermined sites. Consequently, the proton reduction kinetics are accelerated. As a result, the synthesized EHTD-CN exhibits a significantly enhanced hydrogen production rate of 3.09 mmol g(-1) h(-1), which is 30.9-fold higher than that of bulk g-C3N4. Importantly, the underlying mechanisms of improved exciton dissociation and charge dynamics by the tailored electronic structure are thoroughly characterized and elucidated. This work provides new insights into DFT-guided photocatalytic material design for energy and environmental applications.

The rational construction of a reverse hydrogen spillover channel within the catalyst effectively accelerates hydrogen evolution reaction (HER) kinetics, whereas the driving forces and mechanisms that control hydrogen surface migration remain insufficiently investigated. Therefore, we constructed a strongly coupled RuOx-Mo2C cluster-cluster heterostructure catalyst to effectively induce the reverse hydrogen spillover effect. Owing to the high-density accessible active sites and efficient mass transport pathways provided by the strongly coupled cluster structure, hydrogen can migrate directionally and rapidly from Mo2C sites to RuOx sites via the reverse hydrogen spillover effect. This well-defined interfacial coupling and functional partitioning substantially reduce the integrated energy barrier for water dissociation, H* transport, and H-H coupling, leading to drastically accelerated HER kinetics and excellent electrocatalytic activity toward hydrogen evolution. It exhibits an overpotential of only 15 mV at 10 mA cm-2. Moreover, the catalyst maintains stable performance for up to 1000 h under continuous electrolysis without significant degradation, demonstrating outstanding structural and catalytic stability. Furthermore, an anion exchange membrane water electrolyzer with RuOx-Mo2C as the cathode delivers superior catalytic activity, exhibiting a cell voltage of 1.76 V at 1.0 A cm-2 and long-term stability over 1500 h, holding great promise for industrial high-current applications.

The rational construction of heterogeneous interfacial engineering presents a critical strategy for advancing efficient electrochemical water-splitting development. Here, a bimetallic sulfide-coupled MoNi alloy heterostructure catalyst (VMoS/MoNi) is synthesized via hydrothermal and sulfidation methods for high-performance alkaline water electrolysis. Benefiting from interfacial coupling within the VMoS/MoNi catalyst, the active sites are enriched, and electron transfer is promoted, leading to enhanced synergy and collaboration in electrocatalytic reactions. As a result, at 10 mA·cm−2, the VMoS/MoNi catalyst demonstrates excellent HER (26 mV) and OER (223 mV) performance. VMoS/MoNi catalysts used as double electrode in an alkaline electrolytic assembly are noteworthy for achieving a cell voltage of 1.56 V at 10 mA·cm−2, a significant improvement above most previously reported bifunctional electrocatalysts. This result provides further momentum for the design of heterostructure electrocatalysts, advancing the study of renewable energy conversion and storage.

Implementing the hydrogen economy requires reducing the energy costs of electrocatalytic water splitting, thus making it crucial to design low-cost and high-efficiency electrocatalysts to minimize the needed overpotential for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Here, we propose a non-noble metal bifunctional electrocatalyst (HS Co3S4) with a high-spin state by adjusting the coordination structure of spinel sulfide (Co3S4). An analysis based on crystal field theory, molecular orbital theory, and density functional theory revealed that the unpaired electrons in the low-coordination Co in HS Co3S4 occupied the high-energy eg* orbitals, resulting in a high-spin state. This unpaired electron in a high-spin state accelerates the transfer of electrons from the catalyst to the reaction intermediate, reducing the activation energy required for the electrocatalytic reaction and facilitating the HER and OER. The developed HS Co3S4 catalyst requires overpotentials of 70 and 222 mV to drive a current density of 10 mA cm-2 for HER and OER, respectively. An anion exchange membrane water electrolyzer with this catalyst requires only 1.78 V to achieve an industrial-level current density of 1 A cm-2, and it can operate stably for 1000 h. This work provides a promising strategy to regulate the electron spin state of low-cost catalysts for large-scale hydrogen production.

The strong perturbation of the valence band within the entire material system and accelerated *OH dissociation from Fe site are triggered by incorporating CrN4 moiety with low Fenton effect and *OH adsorption energy. This atomically dispersed Cr=N-2=Fe electrocatalyst is developed by adopting a super time-/energy-saving Joule heating strategy (similar to 10 s). Through the investigation of valence orbital energy levels and valence electron behavior for the prepared catalysts, in combination with in-situ Raman testing and theoretical calculations, we have determined that the interaction between the metal sites and oxygen-containing intermediates primarily depends on orbital energy levels before being further evaluated by bond order involving electronic modulation. This finding may offer a valuable insight for future research in related electrocatalysis fields. The Cr=N-2=Fe catalyst exhibits higher ORR catalytic capability than commercial Pt/C, thus driving stable operation of the assembled zinc-air battery for over 300 h.

Hydrogen evolution reaction (HER) in alkaline media demands cost-effective and highly active electrocatalysts to replace noble metals. Herein, we report a ternary MoS₂/Ni₃S₂/Ni(OH)₂ nanoflower composite supported on nickel foam (NF) via a facile one-step electrodeposition strategy. This method enables precise control of MoS₂ morphology while mitigating aggregation-induced active site blockage. The synergistic interplay among MoS₂ (exposing edge sites), conductive Ni₃S₂, and Ni(OH)₂ (modulating electronic structure) significantly enhances HER kinetics. Notably, the optimal catalyst (5-min deposition) achieves ultralow overpotentials of 48 mV at 10 mA cm⁻² and 175 mV at 100 mA cm⁻² in 1.0 M KOH, surpassing most reported Ni- or Mo-based catalysts. Furthermore, it exhibits exceptional stability with negligible activity loss after 5000 cycles and 72-hour continuous operation. XPS analysis reveals that a high Mo⁴⁺/Mo⁶⁺ ratio facilitates electron delocalization, accelerating hydrogen intermediate desorption. This work establishes a new paradigm in HER catalyst design through interface-engineered ternary systems. By unifying electronic synergy theory with the SPRE synthesis method, we overcome the activity-stability trade-off plaguing binary catalysts. The demonstrated 500-hour stability at industrial current densities (100 mA cm⁻²) positions this approach as a transformative solution for scalable green hydrogen production.

Developing highly active and cost-effective catalysts for the hydrogen evolution reaction (HER) is crucial for alkaline water electrolysis, but it remains a significant challenge. Herein, nickel (Ni) nanoparticles composite partially confined in molybdenum dioxide (MoO2) lattices was developed via a facile strong metal–support interaction (SMSI) tuning strategy. Experimental analyses revealed that the regulation of the electronic structure of Ni@MoO2 by SMSI significantly alleviated the work function of Ni@MoO2, accelerating electron transfer and optimizing adsorption of hydrogen intermediates, thereby boosting the HER activity. The optimized Ni@MoO2 catalyst exhibited an overpotential of only 18 and 30 mV to reach a current density of 10 mA cm−2, in alkaline freshwater and seawater, respectively, surpassing the commercial Pt/C catalysts. A two-electrode system with Ni@MoO2 as a cathode required a voltage of 1.46 V to attain the current density of 10 mA cm−2, with no performance degradation after 500 h. This two-electrode configuration exhibited a solar-to-hydrogen conversion efficiency of up to 20.10

Designing and fabricating well-defined heterointerface catalysts with high electrocatalytic performance for the hydrogen evolution reaction (HER) remains a huge challenge. Here, the bicontinuous nano-heterostructure consisting of ultrathin Ni4N/Ni3N particles on hollow tubular carbon fibers was fabricated, and it exhibits superior catalytic activity with a very low overpotential of 75 mV@10 mA cm-2 for HER and stable performance for over 50 h. Theoretical calculation results revealed that the built-in interfacial electric field (BIEF) is formed due to the distinct lattice arrangements and uneven charge distribution in biphasic metal nitrides. The BIEF promotes the electron localization around the interface and enables high valence Ni and more exposed binding sites on the surface of Ni4N/Ni3N/NiO/CFs to accelerate the HER. Meanwhile, the pore connectivity effects facilitate the full exposure of the optimized Ni4N/Ni3N heterointerface, which possesses enhanced intrinsic catalytic activity as active sites. Moreover, the pore connectivity microstructure of the Ni4N/Ni3N/NiO/CFs is conceptualized and verified through the utilization of three-dimensional tomograph reconstruction technology. This study offers new insights into constructing heterostructure interfacial catalysts with three-dimensional spatial precision and provides strong references for practical applications in electrocatalytic hydrogen generation techniques.

ABSTRACT Ruthenium (Ru)‐based electrocatalysts show great promise as substitutes for platinum (Pt) for the alkaline hydrogen evolution reaction (HER) because of their efficient water dissociation capabilities. Nevertheless, the strong adsorption of Ru–OH intermediates (Ru‐OHad) blocks the active site, leading to unsatisfactory HER performance. In this study, we report a universal ligand‐exchange strategy for synthesizing a MOF‐on‐MOF‐derived FeP–CoP heterostructure‐anchored Ru single‐atom site catalyst (Ru‐FeP‐CoP/NPC). The obtained catalyst shows a low overpotential (28 mV at 10 mA cm−2) and a high mass activity (9.29 A mg−1 at 100 mV), surpassing the performance of commercial Pt/C by a factor of 46. Theoretical studies show that regulating the local charge distribution of Ru single‐atom sites could alleviate surrounding OH− blockages, accelerating water dissociation and facilitating hydrogen adsorption/desorption, thus enhancing HER activity. This work aims to inspire further design of highly active and durable electrocatalysts with tailored electronic properties for high‐purity hydrogen production.

Cobalt-based catalysts have demonstrated promising performance in both the oxygen reduction/evolution reaction (ORR/OER), positioning them as potential dual-functional catalysts for recharging Zn-air battery. However, the long-standing challenge remains in achieving satisfactory dual-functionality and stability of these cobalt metal centers. Herein, bicontinuous structured nanofibers composed of multiscale cobalt embedded in asymmetric B/N-coordination carbon (denoted as CoBNPCF-900) are constructed, exhibit enhanced ORR/OER activity, and enable the effective operation of zinc-air battery. The utilization of 3D tomograph reconstruction and absolute permeability experiment simulation unravels a "pore connectivity" effect from visualizing the intricate internal porous structure and comprehending the fluid flow within internal passages. Theoretical calculations further elucidate the electronic transfer tendency and spin polarization of CoBNPCF-900, providing a rationale for the improved performance resulting from alterations in the electronic environment surrounding active Co sites embedded in asymmetric B/N-coordination carbon. A homemade rechargeable zinc-air battery using CoBNPCF-900 as the air cathode exhibits a bifunctional overpotential of 0.808 V and a battery lifetime exceeding 1706.6 h, which is superior to that of the Pt/C+RuO2 catalysts (526 h). This study offers new insights into constructing catalysts with 3D spatial precision and provides strong references for practical applications in energy storage and conversion electrocatalysts.

Rechargeable zinc-air batteries (RZABs) are considered an alternator for the most promising next-generation energy devices. However, their practical application is significantly hindered by the sluggish kinetics of the air electrode. It is crucial to develop efficient electrocatalysts with long-term durability and cost-effectiveness to address these challenges. Here, a bicontinuous nanoflake structure composed of the multiscale activated Fe, Ni nanoparticle, and functionalized B, N-doped carbon support (FeNiBNPCF900 degrees C) is synthesized and validated using 3D tomography reconstruction technology, in which this unique bicontinuous structure offers abundant active sites and rapid mass transfer capability based on a cavity confinement effect. Furthermore, 3D tomography reconstruction and absolute permeability simulation experiments are employed to visualize this intricate internal porous structure and comprehend the electrolyte flow within the internal channels. Therefore, FeNiBNPCF900 degrees C achieves excellent oxidation activity and an ultralow degradation rate benefiting from the synchronously optimized microstructure and demonstrates an ultra-long stability of 1761 h when acting as the air cathode in a homemade RZAB, which is superior to that of the Pt/C&RuO2 catalysts (258 h). This study offers a unique perspective on visualizing the bicontinuous structure effect of carbon-based electrocatalyst with the internal pore network and simulating its electrolyte flow, greatly improving the practicality of RZABs.

Interfacial engineering is critical for efficient charge extraction in perovskite solar cells. However, conventional molecular passivation or lower-dimensional modulation at the buried interface suffers from stress mismatch and weak dipole interaction. Herein, we report an innovative approach involving the in situ construction of a two-dimensional ferroelectric interfacial layer to boost the built-in field and enhance charge extraction. Moreover, the interlayer also acts as a template for the epitaxial growth of 3D FAPbI3 crystals, resulting in the formation of a highly oriented 3D perovskite film with reduced strain and defect density. The optimized rigid device achieves an impressive power conversion efficiency of 26.32% (certified at 25.60%) with a near-radiative-limit V OC of 1.20 V, and the flexible counterpart achieves remarkable efficiency of 25.01%. This strategy simultaneously solves the critical challenges of defect passivation, crystallographic control, and polarization-enhanced charge dynamics, establishing a versatile interfacial engineering paradigm for perovskite solar cells.

Rational construction of heterogeneous interfaces is a key synthetic strategy to enhance the efficiency of NiMobased catalysts for long-term stable electrochemical water splitting technique. However, challenges remain in synthesize technology for polymetallic compound catalysts which integrated multiply advantages from different metal ions. In this study, a selenized MoNi-based V doped electrocatalyst (V-NiMoSex) was proposedly synthesized via a hydrothermal method for high-performance alkaline water electrolysis, which the dopped V ion causes the lattice expansion and alter the d-band center up, facilizing the hydrogen adsorption and evaluating the hydrogen evolution reaction. The incorporation of vanadium and interfacial coupling in V-NiMoSex also enriches active sites and enhances electron transfer, thereby accelerating the water splitting process. Electrochemical data reveal that at a current density of 10 mA cm-2, the oxygen evolution reaction (OER) overpotential of V-NiMoSex in alkaline freshwater is 131 mV, while the hydrogen evolution reaction (HER) overpotential is 37 mV. In an alkaline three-electrode system, the catalyst showed negligible current density decay after 320 h of stability testing. When used as a bifunctional electrode in an alkaline electrolytic cell, the V-NiMoSex catalyst achieved a cell voltage of only 1.54 V at a current density of 100 mA cm-2, significantly lower than most reported electrocatalysts. This low-cost and unique polymetallic selenide catalyst developed in this study offers an innovative solution for designing efficient and stable heterogeneous catalysts for water splitting technique.

Electrocatalytic CO2 reduction using single-atom catalysts (SACs) has emerged as a promising strategy for sustainable fuel generation and addressing environmental challenges caused by CO2 emissions. However, the lack of strategies capable of independently regulating the adsorption energies of *COOH and *CO intermediates remains a significant barrier for SACs in overcoming scaling relationships and enhancing catalytic kinetics. Herein, we report a local strain-induced strategy to establish tandem synergy between Ni single atoms (SA) and NiO atomic clusters (AC), enabling precise modulation of the NiNx- O electronic configuration and intermediate adsorption behavior. In an alkaline flow cell, the Ni-SA/NiO-AC catalyst achieves an impressive CO current density of 226.1 mA cm-2 at -0.92 V (vs RHE) and a remarkable CO Faradaic efficiency of 98.2 %, outperforming both NiSA and Ni/NiO nanoclusters. Density functional theory (DFT) calculations combined with operando attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) revealed that the SA-AC heterogeneous dual-site tandem exhibit a low energy barrier for *COOH formation and independently promote the efficient desorption of *CO. These findings highlight the critical role of strain engineering in enabling tandem synergistic regulation between SA and AC, providing valuable insights for the design of advanced electrocatalysts.

Here we synthesize a high-density active-site three-dimensional (3D) tubular Co3N/CFs catalyst by adjusting carbon fibers (CFs) content. The Co3N/CFs catalyst composed of high-density activated Co3N active site serves as efficient electrocatalysts for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting. The micro-structure of the high-density active-site Co3N/CFs is conceptualized and validated using three-dimensional tomograph reconstruction technology. The high-density active-site structure provides a plentiful number of active sites and efficient mass transfer capability. Moreover, 3D tomograph reconstruction and absolute permeability experiment simulation were innovatively employed to visualize the intricate internal porous structure and comprehend the fluid flow within internal passages. Therefore, the micro-structure of synchronously optimized Co3N/CFs achieves excellent oxygen HER/OER activity and an ultralow degradation rate. A homemade water decomposition device using high-density active-site Co3N/CF also conveys high overall water splitting performance (1.58 V@10 mA cm-2), which is 60 mV lower than that of the (-) 20 wt% Pt/C|| RuO2 (+) benchmark (1.64 V). This study offers a unique perspective on high-density active-site Co3N/CFs through the visualization of the perfect Co3N/CFs micro-structure, internal pore network, and simulation of fluid flow.