Ammonia production via the eco-friendly electrochemical nitrate reduction is an emerging area. The lattice modification of pure copper, an important catalyst, remains under-investigated for broad applications. In this study, we present copper nanoparticles with a distorted and defective lattice structure, derived from the electrochemical transformation of multiphase copper molybdate. These defective and distorted nanoparticles exhibit highly efficient nitrate reduction across a wide potential range, achieving >80% Faradaic efficiency from -0.4 to -1.0 V with a peak efficiency of 94.6% at -0.8 V, notably over eight times higher than Cu powder, reaching an ammonia yield of 52.2 mg & centerdot;h(-1)& centerdot;mg(cat)(-1). Theoretical calculations reveal lattice compression, in conjunction with Cu vacancies, shifts the d-band center away from the Fermi level. Additionally, the localized electrons modulate intermediate adsorption on the copper surface, facilitating a balance between the adsorption and desorption of intermediates. This research not only systematically explores the evolution of molybdate and its impact on copper lattice transformation but also advances the development of nitrate reduction catalysts.

The commercialization of aqueous zinc-metal batteries is fundamentally limited by the intrinsic thermodynamic instability of Zn anodes in aqueous electrolytes and non-uniform Zn2+ flux at the electrode-electrolyte interface, which synergistically drive dendrite growth and parasitic side reactions. To address these challenges, an ionic microenvironment engineering strategy was proposed to simultaneously reconstruct the electric double layer and stabilize the interfacial chemical environment. By introducing borax (Na2B4O7, NBO) as a dual-functional electrolyte additive, the obtained B(OH)4- ions from the hydrolysis of NBO preferentially adsorbs onto the Zn surface to exclude reactive H2O from the inner Helmholtz plane (IHP), thereby homogenizing Zn2+ deposition. Concurrently, the dynamic equilibrium between B(OH)4- and H3BO3 establishes a pH-buffering network that mitigates electrolyte alkalization and suppresses OH--mediated byproducts. This dual regulation achieves dendrite-free Zn plating/stripping for 3800 h in symmetric cells (5 mA cm-2/1 mAh cm- 2). The practical relevance is further demonstrated in Zn||I2 full cells, which retain 78.81% capacity after 9000 cycles at ultrahigh iodine mass loading (5.5 mg cm- 2). This work provides a universal design principle for stabilizing reactive metal anodes through coupled EDL and chemical microenvironment control.

Two-electron aqueous Zn-I2 batteries deliver doubled cathode capacity yet remain constrained by the thermodynamic instability of I+ and sluggish, multistep interfacial kinetics. By systematically correlating electrochemical behavior with ZnCl2 concentration, we demonstrate that strengthened Cl- coordination mitigates ICl hydrolysis but concurrently aggravates charge-transfer resistance. Thus, suppressing hydrolysis alone proves insufficient, underscoring the need to address interfacial kinetics. To address this, we design a single-atom catalytic confinement host featuring atomically dispersed Co-N4 sites on N-doped carbon hollow nanospheres (CoSAs@NC). These isolated Co sites strongly chemisorb polyiodides, expedite electron exchange, and facilitate Zn2+ transport within a hierarchically mesoporous framework, coupling high stability with fast kinetics. Operando spectroscopy and kinetic analyses reveal that atomic catalysis significantly decreases the Tafel slope, enhances exchange current density, and reduces charge-transfer resistance. With high-iodine-content cathode, Co-SAs@NC-based cells achieve 190.6 mAh g-1 at 30 A g-1, and ultralong cycling stability with only 0.00179% capacity decay per cycle over 20000 cycles. Pouch cells deliver high energy density of 218.6 Wh kg- 1 (based on total electrode mass). This integrated catalysis-confinement strategy resolves the intrinsic stability-kinetics trade-off, advancing practical, high-rate Zn-I2 energy storage.

The prevalence of bulky cation hydration shells in aqueous electrolytes often leads to sluggish cation transport and aggressive interfacial reactions. Here, we propose an amphiphile confined water electrolyte in which the aqueous phase reorganizes into nanoscale domains within an amphiphilic matrix, resulting in decoupling of the cation transport in water channels from the inert amphiphile phase. To achieve this, molecular screening converged on linear n-alkanols that combine one hydroxyl head (-OH) with a hydrophobic n-alkyl [-R(CH2)-CH3] tail. The hydrophilic head effectively binds with the water molecules residing around the cations and disrupts the water hydrogen-bond network, whereas the hydrophobic tails pack into a continuous matrix that expels excess water from the bulk phase. Via further tuning of the water-to-amphiphile ratio, nanometric water channels at a size of ∼1.8 nm are formed, yielding a Zn2+ transference number of 0.79. The Zn||KFeMnHCF full cell was able to cycle for 15,000 cycles with a capacity retention of 78.4%, and a discharge capacity of 68.4 mAh/g can be delivered even at -60 °C. This work demonstrates a successful application of amphiphile-driven structuring to confine the aqueous phase in an electrolyte, providing a viable route to mitigate cation migration penalties and reduce water parasitic reactions.

The sluggish kinetics of oxygen reduction and evolution reactions (ORR/OER) severely limit metal-air battery performance. Here, we employ first-principles calculations to systematically elucidate the role of nanotube curvature in tuning catalytic activity. By establishing the structural and electronic feasibility of boron nitride nanotubes (BNNTs) as electrocatalysts through a comprehensive analysis of cohesive energies, curvature energies, and density of states. Subsequently, we explore the catalytic performance of Cu-doped BNNTs with varying diameters, followed by an evaluation of Cu-doped BN monolayers and nanotubes for ORR/OER under strain, with consistent B-N configurations. Curvature not only enhances the catalytic activity but also circumvents the conventional scaling relationships that typically limit activity optimization. Tensile strain modulates catalytic properties by shifting the d-band center at the active site, whereas curvature exerts a more profound influence by redistributing the energy splitting among d-orbital sublevels. Notably, curvature induces a dramatic inversion of orbital energy ordering, whereby the d z 2 ${d_{{z^2}}}$ orbital shifts from the highest to the lowest energy level, and the degeneracy of the dxy and d x 2 - y 2 ${d_{{x^2} - {y^2}}}$ orbitals are lifted. These changes alter the binding modes, effectively breaking the linear relationship between intermediates. This study provides new insights into the microscopic mechanisms of curvature effects on catalytic activity.

The development of catalysts enabling highly efficient oxygen reduction (ORR) and oxygen evolution (OER) reactions is crucial for metal-air batteries. We theoretically explore the catalytic activity of a single atom catalyst, S4Ni@C60. The density functional theory (DFT) results show that strain engineering enhances catalytic performance, with ultra-low overpotentials of eta ORR/OER/Bi= 0.23/0.345/0.575 V for 15% strain. The enhanced activity is attributed to the shift in Ni' d-band center improves, leading to stronger ORR activity and suppressed hydrogen evolution reaction. This study provides insights into optimizing electrocatalysts through strain engineering.

Acidic Zn||MnO2 batteries offer exceptional promise for grid-scale storage due to high theoretical energy and power densities, yet their practical deployment is fundamentally limited by conflicting proton activity requirements at the electrodes: the MnO2 cathode demands high H+ concentration to drive reversible two-electron Mn2+/MnO2 conversion, while the Zn anode suffers severe hydrogen evolution corrosion (HEC) under these conditions. We resolve this incompatibility by designing a dynamically regulated weak-acid electrolyte using strategically introduced Br & oslash;nsted bases. The tuned proton affinity kinetically suppresses acid dissociation at the Zn/electrolyte interface to mitigate HEC, while sustaining high-voltage Mn2+/MnO2 conversion at the MnO2 cathode. This intrinsic kinetic regulation achieved without electrolyte decoupling, protective interphases, or uncontrolled pH drift enables designed Zn||MnO2 cells to achieve an ultrahigh energy density of 951 Wh kg-1 (based on MnO2 cathode mass) and exceptional cycling stability (80% capacity retention after 200 cycles at 0.5 A g-1). This work establishes a practical, scalable electrolyte platform for durable high-performance Zn||MnO2 batteries.

Spider silk's remarkable mechanical properties arise from its hierarchical organization, where β-sheet nanocrystals confer strength and amorphous chains impart extensibility. However, replicating this performance in synthetic fibers has been hindered by the challenges of expressing high-molecular-weight spidroins and processing them into fibers. Here, we overcome these limitations by engineering a mini-spidroin (∼33 kDa) that is both easily expressible and spinnable, yet yields fibers with exceptional strength and toughness. Our strategy introduces cysteine residues at the termini of polyalanine (polyA) segments, enabling inter-strand disulfide bonds that enhance molecular cohesion during liquid-liquid phase separation (LLPS). This "edge-cysteine locking" promotes directional β-sheet assembly under extensional flow, resulting in fibers with an ultimate tensile strength of 531 ± 33 MPa and toughness of 182 ± 6 MJ/m3, surpassing many bulkier (>100 kDa) recombinant spidroins. Molecular dynamics simulations indicate that disulfide bonds reinforce inter-strand interactions and prevent chain slippage under shear. By demonstrating that a small, easily produced protein can outperform larger, harder-to-process analogs, this work establishes a scalable and efficient route to high-performance biomimetic fibers, advancing both scientific understanding and practical applications of artificial spider silk.

Aqueous redox flow batteries are promising for long-duration energy storage. However, many of them (e.g. sulfur-based and organic-based flow batteries) suffer from sluggish kinetics with low energy efficiency and insufficient capacity utilization. Here, we propose relay catalysis as a universal strategy to achieve high reaction rates while minimizing overpotential, enabling high capacity and energy efficiency. Inspired by sequential electron transfer in cellular respiration, relay catalysis employs a low-overpotential catalyst (e.g., isoalloxazine) to initiate the reaction, seamlessly transferring control to a high-activity catalyst (e.g., quinone) to sustain charge propagation, breaking the trade-off between overpotential and catalytic rate. Using this strategy, we demonstrate polysulfide-ferrocyanide flow batteries with near full polysulfide utilization (S42-/S22-, 64 Ah L-1negolyte) and high stability over 3 months (> 500 cycles at 20 mA cm-2, decay rate 0.00071% per cycle, 0.003% per day). We further extend this strategy to organosulfide- and azo-based batteries with various relay-catalyst couples. By mimicking biological electron relays, this approach not only redefines homogeneous catalysis for energy storage but also establishes a transformative platform for designing flow batteries with enhanced performance and scalability.

Many marine sessile organisms achieve robust underwater adsorption through 3,4-dihydroxyphenylalanine (Dopa)-independent strategies, yet the underlying self-assembly mechanisms remain elusive. Here, we decipher the Ca2+-triggered interfacial adsorption of a sea anemone thrombospondin-1 type I repeat-like (TSRL) protein, identifying its tyrosine-rich T3 subunit as the core mediator for coating formation. The fabricated T3 coatings exhibited strong wet adsorption stability, biocompatibility, and intrinsic antioxidant activity. Mechanistically, T3 self-assembly is driven by favorable enthalpy, initiating with nanosphere aggregation and forming hierarchical fishnet-like microstructures. Molecular dynamics simulations revealed that, unlike the rapid collisions of T1 subunit, the slower diffusion of T3 enables precise orientation and pairing, leading to a marked increase in inter-residue contacts dominated by cation-π interactions between lysine and tyrosine residues, alongside π-π stacking. Mutant studies confirm that disrupting these interactions impairs both self-assembly and interfacial adsorption, establishing positioned tyrosine residues as molecular stickers. Together, these findings establish a tyrosine-mediated, non-Dopa marine adsorption paradigm and highlight the T3 protein as a promising biomaterial platform for tissue engineering and antioxidant biomedical applications. STATEMENT OF SIGNIFICANCE: This work reports a tyrosine-driven, Dopa-independent wet adsorption paradigm in marine biological systems, fundamentally expanding the current understanding of underwater adsorption mechanisms. The discovery that precisely positioned tyrosine residues can orchestrate hierarchical self-assembly through specific π-π and cation-π interactions establishes a new conceptual framework for designing bioinspired coatings. Beyond its fundamental implications, this system offers a versatile combination of robust wet adsorption and inherent biocompatibility, addressing a critical challenge in biomedical adhesive development. Moreover, the intrinsic reactive oxygen species (ROS)-scavenging capacity positions this protein-based platform as a multifunctional biomaterial with promising applications in wound healing, tissue engineering, and antioxidant therapeutics.

Aqueous Zn-iodine batteries with multi-electron transfer are promising for energy-dense storage systems. However, the low conversion efficiency and slow kinetics of the I2/IO3- conversion in current systems impair their performance. Herein, we report a cost-effective and mild electrolyte containing Zn(OAc)2 and Ba(OAc)2, free of strong acids/alkalis and extraneous halide ions (e.g., Cl- and Br-), enabling high reversibility and fast kinetics of the six-electron I-/I2/IO3- redox cascades. Specifically, OAc- anions successfully activate the I2/IO3- conversion, while Ba2+ cations facilitate this process and act as an electrostatic shielding layer to modulate uniform Zn deposition. Consequently, the Zn||Zn symmetric cells exhibit an ultralong lifespan of 2800 h in Zn(OAc)2 + Ba (OAc)2 electrolyte-46-fold longer than in Zn(OAc)2 (0.25 mA cm-2, 0.25 mAh cm-2). Furthermore, Zn||I2 coin cells achieve exceptional cyclability: 1600 cycles at 6 mA cm-2 with 99 % average Coulombic efficiency. By circumventing the traditional reliance on halide intermediates, this work achieves highly reversible six-electron I-/IO3- conversion-establishing a new paradigm for designing energy-dense battery systems.

Decoupling Li+ transport from polymer segmental dynamics is crucial for enhancing ionic conductivity (sigma) and transference number (t+) in solid polymer electrolytes (SPEs). Herein, by studying four ether-based SPEs with varying oxygen density, we identify a transition from polymer relaxation-limited ion transport in poly(ethylene oxide) (PEO) to ion hopping-dominant transport in poly(tetrahydrofuran) (PTHF), poly(1,3-dioxolane) (PDOL), and poly(trioxymethylene) (PTOM). Molecular dynamics simulations and solid-state 7Li nuclear magnetic resonance reveal origins of the transition. In PTHF, weak solvation with lithium bond characteristics contributes to a less-shielded Li+ environment, while in PDOL and PTOM, the discontinuous coordination (DC) structure and multi-chain binding are pivotal. The presence of DC structures is experimentally confirmed by in situ attenuated total reflection Fourier transform infrared spectroscopy and supported by quantum chemistry calculations. As a result, PDOL and PTOM exhibit t+ values exceeding 0.5 and enhanced sigma values of 4.3 x 10-3 and 8.5 x 10-3 S cm-1 at 373 K, respectively. The Li/SPEs/LiFePO4 cell with ex situ-prepared PDOL achieves a superior capacity retention of 90.8% after 50 cycles. This work underscores the significance of functional group spacing in tuning the transport mechanisms and demonstrates how the decoupling strategy can guide the bottom-up design of advanced SPEs.

The CO2-to-CO reduction behaviour on Fe/Co/Ni-based single-atom catalysts was systematically investigated. *CO is preferentially stabilized relative to *COOH under increasingly negative interfacial electric fields. A pH-dependent volcano relationship is revealed, exhibiting a rightward shift with increasing pH due to the distinct dipole moments of *CO and *COOH. Benchmarking against experimental data validates the microkinetic volcano model and identifies promising catalyst candidates. Importantly, dipole-field interactions emerge as a general descriptor, bridging theoretical predictions and experimental observations in CO2RR and beyond.

Designing humidity-responsive protein fibers that combine high recovery stress with structural integrity is essential for advancing soft actuators under physiological conditions. However, conventional polymer-based actuators are limited by low mechanical strength and poor humidity tolerance. Spider silk provides a natural model for water-responsive actuation, yet replicating its performance in recombinant systems remains challenging due to hydration-induced β-sheet disruption and insufficient crystalline stabilization. Here, recombinant spidroin fibers are engineered by introducing terminal cysteine crosslinking, enabling site-specific disulfide bonds to form during shear-assisted wet spinning. This covalent edge reinforcement preserves β-sheet alignment even at 90% relative humidity, as confirmed by molecular dynamics simulations and spectroscopic analyses. The optimized C4S fibers exhibit reversible and controllable humidity-driven actuation, delivering rapid contraction with a recovery stress of 45 MPa and a work density of 122 kJ m-3, exceeding typical synthetic actuators and surpassing human skeletal muscle by over threefold. This sequence-encoded crystalline locking strategy provides a generalizable molecular design for creating moisture-resilient, high-performance protein actuators, with potential applications in soft robotics, adaptive textiles, and biomedical devices.

Sodium superionic conductor (NASICON)-type materials are promising cathodes for sodium-ion batteries due to their stable multi-channel frameworks and exceptional ionic conductivity. Among them, Na3V2(PO4)2F3 (NVPF) has attracted significant attention. However, the low electronic conductivity and phase impurities limit its sodium storage capability. Herein, we present a Fe and Mn dual-doped NVPF (FM-NVPF) cathode with improved phase purity, electronic conductivity, and electrochemical activities. Detailed ex-situ analyses and density functional theory calculations reveal that Fe and Mn dopants induce defect energy levels and modulate the electronic structure, resulting in a direct-to-indirect bandgap transition in NVPF, which in turn increases carrier concentration and lifetime, accelerates ionic/electronic transport, and improves structural stability. As a result, the FM-NVPF cathode delivers a high capacity of 126.6 mAh g⁻1 at 0.1 C (1 C = 128 mAh g⁻1) and outstanding high-rate capability of 67.6 mAh g⁻1 at 50 C, corresponding to 1.2 min per charge. Furthermore, Na ion full cells assembled with the FM-NVPF cathodes and hard carbon anodes exhibit a high energy density of about 175 Wh kg−1cathode+anode mass and appealing cyclic stability. This work provides an efficient strategy for developing high-purity and high-performance NVPF cathode materials for advanced sodium-ion batteries.

Hydrogel electrolytes, owing to their intrinsic biocompatibility and mechanical flexibility, hold great promise for next-generation flexible zinc-ion batteries (FZIBs). However, the fundamental understanding of how mechanical deformation influences Zn2+ transport dynamics remains elusive. Herein, we unveil the strain-mediated ion selectivity mechanism in Zn(OTf)2/PAM/H2O hydrogel electrolyte via molecular dynamics simulations, revealing that the Zn2+ transference number (t.) increases from 0.37 to 0.53 under 0%-200% strain, despite a decrease in ionic conductivity within one order of magnitude. This anomalous behavior is attributed to a modulation of the secondary solvation structure. First, strain disrupts the water-dominated hydrogen-bond network (the H-bonds per H2O from 2.00 to 1.77), leading to weakened PAM-H2O interactions and strengthened PAM-Zn2+ coordination (Delta CN = +0.8). Furthermore, it promotes the proportion of Zn2+ ions coordinating with two or more polymer chains (5.44% to 13.91%). Significantly, a strong negative linear correlation (R2 = 0.94) between the t. and the H-bonds per H2O, establishing a quantitative structure-property relationship that links the microscopic solvation environment to the macroscopic ion selectivity. This study provides fundamental molecular-level insights into the coupling between mechanical strain and ion diffusion behavior, offering a new design principle for high-performance flexible energy storage devices through solvation structure engineering.

Hydration plays a crucial role in modulating the thermal and dynamic behavior of soft porous materials, yet its microscopic impact on molecular-scale nanoporous systems such as porous organic cages (POCs) remains poorly understood. In this work, we employ molecular dynamics simulations to systematically investigate the influence of water content on the glass transition, structure, and mobility of amorphous POC systems. Five model systems with H2O:POC molar ratios ranging from 0 to 40 were constructed, and temperature-dependent simulations were carried out from 203 to 373 K. Our results show that an increase in hydration systematically depresses the glass transition temperature, with Tg decreasing from 325.43 K in the dry system to 279.18 K at a H2O:POC ratio of 40, confirming the strong plasticizing effect of water. Structural analyses show that water initially expands partially collapsed POC assemblies at low hydration, but this effect is saturated at higher water contents because of limited adsorption capacity. Consistently, the number of POC-water hydrogen bonds per water molecule decreases with an increase in hydration, indicating weaker average water-framework affinity. Dynamic analyses reveal a clear crossover from strongly subdiffusive water motion at low hydration, with diffusion exponents (α) as low as ∼0.2, to near-Fickian diffusion at high hydration and increased temperatures, where α approaches 1. Together, these results establish a molecular-level picture of hydration-driven plasticization in amorphous POC systems and provide guidance for designing responsive nanoporous materials with tunable thermomechanical and transport properties.

The oxygen reduction reaction (ORR) is crucial for the development of metal-air batteries. This work systematically investigates the curvature-mediated regulation of ORR performance in asymmetrically coordinated single-atom catalysts, CoN3Cl doped carbon nanotube (CoN3Cl@CTB), using first-principles calculations. By analyzing the binding energy, ab initio molecular dynamics, and density of states confirm the robust stability and metallic electronic properties of these catalysts. Within an optimal curvature range (CoN3Cl@CTB (9, 4) to (14, 4)), the catalysts demonstrate superior performance. Notably, CoN3Cl@CTB (14, 4) achieves an ultralow over-potential of 0.27 V, representing an approximately 40% improvement over commercial Pt/C. Further orbital analysis shows that performance enhancement stems from curvature's precise modulation of Co's coordination environment: it optimizes interfacial charge transfer and, critically, modulates Co dxzand dx2_y2 orbitals in a diameter-dependent way, inducing energy gap separation and decoupling their pi/sigma bonding roles, thus finetuning intermediate adsorption energies for ORR. This study provides important theoretical insights for designing high-performance cathode materials for metal-air batteries.

ABSTRACT Ion‐exchange membranes (IEMs) are essential for efficient and durable flow batteries, yet their inherent conductivity–selectivity trade‐off severely limits flow battery performance. Most conventional strategies to improve selectivity rely on regulating ion diffusion within ion‐exchange channels through size exclusion and electrostatic repulsion, inevitably compromising ionic conductivity. Here we shift the paradigm to ion partitioning at the membrane–electrolyte interface by establishing ion‐specific gating that selectively intercepts active species while preserving rapid charge carrier transport. The developed ultrathin (29 ± 2 µm) polar oxygen‐vacancy‐enhanced (POVE) membrane suppresses polysulfide crossover through strong chemisorption and a strengthened hydration layer, delivering over 3.4 times the selectivity of the base membrane at comparable conductivity and over 24.8 times the selectivity of commercial Nafion membranes. In the polysulfide–ferrocyanide flow battery, it achieved 82% energy efficiency at 40 mA cm −2 and sustained over 2000 cycles with negligible capacity decay, far exceeding 286 cycles for the base membrane and < 100 cycles for Nafion. This work decouples conductivity from selectivity via a scalable interfacial ion‐specific gating strategy, offering a transformative framework for developing affordable, high‐performance IEMs.