Constructing stable and highly active asymmetric Mn-N3 single-atomic sites integrated with Mn nanoclusters remains challenging. This work develops a facile secondary pyrolysis strategy to fabricate a porous dual-site catalyst (MnSA/MnNC-NC) featuring both single-atom Mn-N3 (MnSA) and Mn nanoclusters (MnNC) sites on nitrogen doped carbon black (NC). The MnNC not only stabilizes the MnSA but also enhances the overall conductivity and preserves the hierarchical porous framework, thereby maximizes dual-site exposure and mass transport. This synergy endows MnSA/MnNC-NC with outstanding activity for bifunctional oxygen catalysis with half-wave potential of 0.91 V and onset potential of 1.59 V, both surpassing those of commercial noble metal Pt/ C and RuO2. A liquid zinc-air battery (LZAB) assembled with MnSA/MnNC-NC achieves a high power density of 218.0 mW cm-2 and stability exceeding 500 h. Density functional theory (DFT) calculations insightfully reveal the inherent mechanism that MnNC not only stabilizes asymmetric MnSA, but also precisely modulates the electronic structure and d-band energy levels, which kinetically optimizes the desorption behavior of reaction intermediates *OH and thermodynamically lowers the reaction energy barrier. This work verifies the critical role of nanoclusters on asymmetric single-atom sites, offering essential guidance to design of high performance catalysts for energy storage devices.

Cryo-EM enables multimodal characterization of Li and post-Li metal anodes and interphases, offering mechanistic insights for next-generation battery design.

Wearable self-powered electronics operating under harsh environments require sustainable dielectric materials combining mechanical robustness, dielectric reliability, and stable triboelectric performance. Here, a spray-assisted biosynthetic co-assembly strategy followed by hot-press densification was developed to construct bacterial cellulose (BC)/mica nanocomposite films with a nacre-inspired layered structure and Janus-like compositional asymmetry across the film thickness. Mica nanosheets introduced during continuous BC growth formed mica-rich and BC-rich regions that remained interconnected by the in situ-grown BC nanofibrous network. The optimized BC/M34 film achieved a tensile strength of 266 MPa and a dielectric strength of 123.8 kV mm − 1, while retaining 76.5% of its tensile strength after 10,000 bending cycles. In a contact–separation TENG, the mica-rich surface generated approximately 75 V, compared with 47 V for the BC-rich surface and 50 V for a homogeneous BC/M34 control, demonstrating a clear dependence of triboelectric output on asymmetric surface organization. The films maintained structural integrity after cryogenic exposure (−196 °C), heating at 120 °C, and 20 thermal-shock cycles. The TENG exhibited only ~2% voltage fluctuation over 5000 cycles and retained distinguishable Morse-code signals after thermal and UV treatments. This work provides a biosynthetic route for integrating nacre-inspired organization, Janus-like compositional asymmetry, dielectric reliability, and triboelectric functionality in sustainable cellulose-based electronics.

The development of polymer electrolytes with high ionic conductivity, robust mechanical strength, and excellent interfacial stability remains a critical challenge for high-performance sodium metal batteries (SMBs). Herein, a "chemical-structural dual regulation" strategy introduces complementary soft and hard segments into a gel polymer electrolyte (GPE), enabling concurrent optimization of solvation structure and mechanical properties. Soft segments with strong electron-withdrawing -CF3 groups form solvent-rich domains that weaken Na+-solvent interactions, while amide N-H groups create polymer-rich domains that enhance mechanical strength and anchor anions via hydrogen bonding, promoting sodium salt dissociation. Benefiting from this rational molecular design, GPE-9 delivers an outstanding ionic conductivity of 1.11 mS cm-1 and a high Na+ transference number of 0.74 at room temperature, and supports long-term cycling of Na||Na symmetric cell at 0.2 mA cm-2 for 7000 h. The Na|GPE-9|Na3V2(PO4)3 (NVP) cell demonstrates excellent rate durability, sustaining 12 000 and 20 000 cycles at 5C and 10C, respectively, with nearly 100% Coulombic efficiency. Furthermore, a 29-layer pouch cell with NVP cathode and hard carbon (HC) anode delivers a high capacity approaching 1.0 Ah. This study demonstrates that designing polymer segments capable of regulating solvation structure and directing interfacial fluorination offers a promising strategy for high-performance GPEs for Na batteries.

Electron microscopy techniques such as electron energy-loss spectroscopy (EELS) facilitate the spatiospectral characterization of plasmonic nanostructures. In this work, a time-dependent perspective is presented that significantly enhances the utility of EELS. In particular, this approach facilitates the analysis of the dynamics of plasmonic excitations that repeatedly interact with swift electrons in a STEM-EELS configuration. This includes the bulk plasmon mode, which can only be excited by penetrating electron beams, and the fundamental surface plasmon polariton modes propagating along the wire, which can be excited by both penetrating and aloof trajectories. In addition, the role of higher-order azimuthal surface plasmon polariton modes, often overlooked for very thin wires, is observed and analyzed in both the energy-loss spectrum and from the dynamical perspective. Such a complete understanding of the interaction of electrons and plasmonic excitations is key for the design of efficient plasmonic sensors, the study of hot electron dynamics in metals, and applications in the context of electron quantum optics, where full control of the spatial and temporal characteristics of the fields at the nanometer and femtosecond scales is highly desirable.

Conversion-type sulfides offer high capacities for sodium storage but are limited by sluggish redox kinetics, incomplete reconversion, and large volume changes. Here we show that these limitations can be addressed through octahedral-site Ni3+ substitution in spinel nickel-cobalt sulfides. By selectively enriching Ni3+ in the octahedral sites of NiCo2S4 to form Ni(Co1- xNix)2S4 (NNCS) hollow nanospheres, the d-band center is downshifted from -1.49 to -1.80 eV and the metal-sulfur d-p hybridization is strengthened, with the d-p energy separation narrowing from 0.289 to 0.103 eV. These electronic-structure changes lower antibonding-state occupancy and facilitate electron transfer during bond breaking and reformation, thereby enabling fast and reversible conversion. Ex situ HRTEM, SAED, XPS, and XRD directly show that NNCS undergoes nearly complete reconversion upon charge, in contrast to the residual metallic species observed in the control sample. The electrode accordingly delivers an initial Coulombic efficiency (ICE) of 91%, 632 mAh g-1 after 800 cycles at 5 A g-1, and 500 mAh g-1 after 900 cycles at 10 A g-1. When assembled into a full cell with Na3V2(PO4)3, the capacity retention after 56 cycles reaches 91.3%.

In this research, a flexible self-supporting zinc-ion hybrid supercapacitor (ZHSC) is prepared using polyvinylidene fluoride (PVDF) as the porous carbon source, and an appropriate amount of graphite powder is added to promote graphitization during the pyrolysis of PVDF at 800oC under N2 atmosphere. The prepared porous carbon material (4GP@CC-800) has a specific surface area of 1420.2m² g-¹. It is used as the positive electrode of a ZHSC, zinc foil is the negative electrode, and 2 mol L-¹ ZnSO4 is the electrolyte. It provides a mass specific capacitance of 607.5 F g-¹ and an areal specific capacitance of 1518.8mF cm-² (mass loading 2.5mg cm-²). The energy density is 534.3 μWh cm-² at a power density of 800 μW cm-². When the cycling number reaches 10,000 charge–discharge loops, the device can maintain 111% of its initial capacity, which is attributed to the activation effect of the carbon material. Notably, when the load is increased to 10.4mg cm-², the device can still maintain the mass specific capacitance at 600 F g-¹, and thus the high load ZHSC device has an areal specific capacitance of 6213.1 mF cm-², and a high energy density of 2209 μWh cm-² at a power density of 800 μW cm-². It can obtain an energy density of 405.3 μWh cm-² even at a power density of 16000 μW cm-², which indicated a practical application value.

This study investigates the role of pi-electron delocalization in tuning the electronic band structures of two-dimensional metal-organic frameworks (2D MOFs), using 9,10-dicyanoanthracene (DCA) on different metal surfaces. While hydrogen-bonded assemblies form on Ag(111), distinct coordination networks emerge on Cu(111) and Au(111): a Kagome-based 2D framework (DCA3Cu2) with flat bands and Dirac cones, and a quasi-one-dimensional chain structure (DCA3Au2), respectively. Density functional theory (DFT) calculations reveal a clear correlation between the extent of pi-delocalization and the electronic properties. As delocalization evolves from localized (DCA3Cu1) to quasi-1D (DCA3Au2) character, the bandgap narrows from 0.07 eV to 0.03 eV. Even in localized and quasi-1D systems, weak inter-unit hydrogen-bonding interactions contribute to electronic band formation, indicating the synergy between coordination and non-covalent interactions in shaping band structures. These findings demonstrate that coordination-controlled pi-delocalization offers a precise pathway to tailor the electronic properties of 2D MOFs.

Palladium (Pd)-catalyzed reactions, such as the Suzuki-Miyaura cross-coupling, have demonstrated significant enhancement when facilitated by hybrid Au/Pd nanostructures. However, the role of gold, through charge transfer or localized heating, remains debated. Moreover, the impact of plasmon excitation on reaction selectivity remains largely unexplored. Herein, we report a facile, two-step, room-temperature synthesis of spiked Au/Pd nanowires for visible-light-driven Suzuki-Miyaura cross-coupling under ambient conditions. The reaction was monitored in situ using liquid-state surface-enhanced Raman spectroscopy (SERS) and ex situ using gas chromatography-mass spectrometry (GC-MS). We systematically studied the cross-coupling of 4-iodothiophenol with phenyl boronic acid under varying excitation wavelengths, laser intensities, external heating, and charge carrier scavengers, revealing the distinct role of non-thermal charge carriers in selectively promoting formation of the biaryl product. In the dark, a temperature of 85 degrees C was required to initiate the reaction, while thiophenol was observed as a major by-product. To further validate the plasmon-induced selectivity, we performed the reaction with 4-iodotoluene entirely in solution and monitored the products using GC-MS. Under light irradiation, cross-coupling was favored over the thermally driven reactions in the dark. This highlights the role of non-thermal charge carriers in enhancing the selectivity of Suzuki cross-coupling under plasmonic excitation.

Metal sulfide anodes offer high theoretical capacities for sodium-ion batteries but are limited by severe chemo-mechanical degradation from conversion/alloying reactions, poor electronic conductivity, and sluggish ion transport. Here, we present a mechanics-led design strategy, medium-entropy ductility engineering, implemented in a ternary thiospinel, ME-NCUS. Density functional theory shows a high Pugh ratio (2.722), elevated Poisson's ratio (0.336), and a reduced Young's modulus (112.8 GPa), collectively indicating an intrinsically ductile, compliant lattice that accommodates elastic strain and dissipates anisotropic stress. This engineered mechanical response mitigates sodiation/desodiation-induced volume expansion, suppresses crack initiation and propagation, and stabilizes electrode/electrolyte interfaces. Correspondingly, the material exhibits accelerated kinetics, with high Na+ diffusivity and markedly lower activation barriers. The result is outstanding durability and power performance, retaining 92% capacity (640 mAh g-1) after 900 cycles at 5 A g-1 (7 C) with robust long-term stability. By quantitatively linking elastic constants to ion-transport barriers and failure tolerance, this work elevates ductility as a primary design handle for high-capacity, large volume change anodes. Medium-entropy engineering thus offers a general and scalable route to entropy-stabilized sulfides and other conversion/alloying anodes, enabling mechanically resilient and kinetically fast sodium storage.

Oxygen incorporation into conjugated polymers is a proven strategy to boost photocatalytic hydrogen evolution by improving hydrophilicity, tuning band structures, and increasing active sites. However, the impact of backbone oxygen content on performance is not fully understood. To address this, we designed four polymers with varying oxygen levels, denoted PBDT-2O, PBDT-4O, PBDT-6O, and PBDT-8O, using benzo[1,2-b:4,5-b']dithiophene (BDT), its tetraoxide derivative (BDTTO), thiophene (T), and 3,4-ethylenedioxythiophene (DOT) as building blocks. Compared to PBDT-2O, the alkoxy side chains in PBDT-4O enhanced hydrophilicity and planar conjugation. Oxidizing the BDT sulfur atoms to sulfonyl groups in PBDT-6O created a donor-acceptor push-pull effect, resulting in a redshifted absorption and narrower band gap. The synergistic combination of disulfonyl and alkoxy functionalities in PBDT-8O delivered the best performance, with a hydrogen evolution rate of 55.52 mmol g- 1 h- 1 and an apparent quantum yield of 2.44% at 600 nm. It also maintained high activity (25.8 mmol g- 1 h- 1) under natural sunlight. Mechanistic studies using femtosecond transient absorption spectroscopy and DFT calculations revealed that this synergy accelerates exciton dissociation, enhances charge separation, and provides more active sites. This work clarifies the role of oxygen content and offers a rational design strategy for efficient polymer photocatalysts in solar energy conversion.

Solid-state batteries (SSBs) are promising candidates for next-generation energy storage due to their high theoretical energy density. However, their practical application is hindered by Li/solid-state electrolyte interfacial issues, including poor contact, lithium dendrites, and side reactions, while polarization under high current densities or areal capacities cannot be ignored. Herein, we report a multifunctional composite interlayer (BN-ASDSI) composed of a flexible polymer scaffold, a sultone-based electrolyte, and boron nitride (BN) to address these challenges. Benefiting from the Lewis acid-base interaction, BN-ASDSI exhibits an anion-anchoring effect that induces a localized microelectric field, accelerating Li+ transport while restricting anion mobility. Concurrently, the solvent-repelling property of BN mitigates interfacial side reactions, synergistically promoting the formation of LiF-rich inorganic solid-state interface to stabilize the Li metal. Notably, the symmetric cell with BN-ASDSI achieves an ultrahigh critical current density of 8.8 mA cm-2. Most impressively, the LiFePO4 SSB delivers stable operation for 1500 cycles at 6 C with a capacity retention >92%, while the high-loading LiNi0.83Co0.12Mn0.05O2 (17.2 mg cm-2) SSB exhibits a high discharge areal capacity of 3.2 mAh cm-2 at 1 C and retains 93% capacity after 80 cycles at 0.33 C, showcasing the practical potential of BN-ASDSI enabled SSBs.

Uncontrolled dendrite growth and electrolyte depletion remain critical barriers to high-rate lithium-metal batteries (LMBs). Here we report a phase-transition, sustained-release strategy that simultaneously stabilizes the Li surface and ether electrolyte. A fluorinated alcohol (1 H,1 H,2 H,2H-perfluoro-1-decanol, HDFD) is briefly melted onto Li foil and cooled to form a conformal F-rich coating. The Li-F/Li-O bonding produces an inorganic/organic bilayer artificial solid electrolyte interface with high modulus and elasticity, while the top solid HDFD reservoir gradually dissolves into ether electrolyte during operation. The dissolved HDFD fragments enter the Li* solvation sheath, lower the desolvation barrier, scavenge the reactive radicals and continually re-heal the interfacial defects. Benefiting from this synchronous protection effect from electrolyte interface and bulk, symmetric cells deliver the unprecedented lifespans of 2000 h at 50 mA cm- 2 and 5 mAh cm- 2, and 3000 h at 30 mA cm- 2 and 30 mAh cm- 2 with suppressed dendrites. Moreover, the stabilized electrolyte enables the LiNi0.8Co0.1Mn0.1O2|| HDFD@Li full cells under high cathode loading of 9.5 mg cm- 2 and high cut-off voltage of 4.5 V to retain highly reversible capacity for 450 cycles at 0.5 C. The facile melt-dip process and self-replenishing behavior of fluorinated coating offer a scalable route toward high-rate and long-life LMBs.

Non-precious triple-site (tri-site) electrocatalysts that combine bimetallic single atoms with nanoparticles are promising for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, we presentg a strategy of precisely constructing a tri-site catalyst, FeCoSA/NP@NGA-600, with a low concentration of metal precursors at a relatively low pyrolysis temperature of 600°C. This catalyst comprises a relatively high density of iron single-atom sites (Fe─N4), cobalt single-atom sites (Co─N4), and small-sized iron-cobalt alloy nanoparticles (FeCoNP), achieving efficient synergistic catalysis. This catalyst also forms a biomimetic hierarchical pore architecture, ensuring sufficient site exposure and fast mass transport, demonstrating outstanding catalysis activity: a 0.93 V half-wave potential for ORR, a 1.54 V overpotential for OER, and a 385 h cycle life in a liquid zinc-air battery (LZAB), better than commercial Pt/C and RuO2. With experimentally-guided construction of tri-site models, theoretical calculations reveal that the inherent synergy is associated with electronic modulation, optimized O2 adsorption, and direct O─O bond cleavage (*OOH → *O + *OH) in ORR kinetically, and a low energy barrier in the rate-determining step thermodynamically. This study contributes an effective approach to design and an insightful understanding of multi-site masterful electrocatalysts containing metals with different coordination abilities.

Recently, a lot of efforts have been devoted into lithium-sulfur (Li-S) battery system due to its high theoretical capacity (1675 mAh g-1) and low cost, which could be a competitive candidate for the next-generation batteries in the future. However, it suffers from a poor cycling stability during charging-discharging, which is blamed to the “shuttle effects” of lithium polysulfides. Fundamental understanding of the formation and dissolution processes of both solid phases, S8 and Li2S, is necessary for the development of advanced cathode materials with improved electrochemical performance. Using colloidal route, complex hybrid carbon nanostructures have been synthesized using colloidal polymeric particle as soft template, which have been applied as cathode materials for Li-S batteries. Synchrotron-based operando high-resolution X-ray imaging has been successfully used for the detailed morphology study of sulfur particles during cycling of the battery cells. Moreover, cryo-TEM has been applied to reveal sensitive electrochemical materials and interfaces, e.g., Li metal and SEI.

Sulfur cathodes have attracted considerable attention due to their potential for high energy density and cost-effectiveness. However, their limited stability, in part stemming from volume changes during cycling and the dissolution and migration of metal polysulfides, has hindered their commercialization. Binders play a critical role in preventing electrode delamination, while potentially contributing additional functionalities, such as trapping polysulfides. In this work, we introduce an aqueous-processable sulfur cathode binder composed of polyvinyl alcohol (PVA) and polyethylene glycol (PEG). Multiple hydrogen bonding interactions provided by the PVA/PEG binder hydrogen-bond network enhance metal-ion diffusion and trap polysulfides, thereby reducing their dissolution. Additionally, microcracks generated during the cycling can be healed by the dynamic hydrogen-bond network. Thereby, in lithium-sulfur cells, PVA/ PEG-based cathodes exhibit an ultralow per-cycle capacity fade of 0.0023% over 600 cycles at 1C, and deliver up to 677 mAh/g in lean-electrolyte pouch cells (E/S = 4lL/mg), retaining 99% of the initial capacity after 100 cycles at 0.1C in pouch cell. Theoretical calculations and molecular dynamics simulations confirm the superior adsorption energy and repairability of the PVA/PEG binder, reinforcing its ability to stabilize the cathode. Additionally, PVA/PEG-based cathodes exhibit excellent flame retardancy, support eco-friendly and closed-loop recycling due to the binder's water solubility, which allows for easy electrode material reutilization. (c) 2026 Published by Elsevier B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

ABSTRACT Transition metal nitrides (TMNs) are attractive for cutting‐edge energy storage technology, especially emerging lithium–sulfur (Li–S) batteries, owing to their electronic structures resembling those of noble metals. Herein, we unveil the underlying mechanism by which TMNs accelerate reaction kinetics, showcasing two nanostructured TMNs (Mo2N and VN) embedded within tailored carbon architectures. A novel, unexplored self‐nitriding approach was developed to synthesize TMNs with precisely controlled solid (sC) or hollow (hC) carbon architectures, achieved through a colloidal route using imidazolium‐based poly(ionic liquid) (PIL) nanoparticles as both a nitrogen‐rich template and morphology‐directing agent. Compact TMN architectures as sulfur hosts enhance ion diffusion and reaction kinetics, enabling efficient active site access and delivering high performance, such as VN@sC with high initial capacity of 792 mAh g−1 at 2 C and cyclability up to 650 cycles. Meanwhile, hollow architectures (VN@hC and Mo2N@hC) featuring hierarchical porous structures serve as cathode electrocatalytic additives, enabling high sulfur loading and delivering an initial capacity of 1143 mAh g−1 at 0.1 C. Remarkably, this performance is achieved with only 5 wt% additive content in scalable 7.9 × 11 cm2 and 12‐layer pouch cells designed for drone power systems.

Lithium-sulfur batteries (LSBs) have bright prospects for advanced energy storage systems, enabled by their remarkable energy content of 2600 Wh kg-1, yet their commercialization remains hindered by polysulfide shuttling and sluggish reaction kinetics. The stepwise and complex evolution of sulfur species renders it difficult for a monofunctional catalyst to effectively facilitate the complete polysulfide redox reactions. This study presents a nanoflower-like ZnSe-MoSe2 bimetallic selenide heterojunction that can adapt to the evolving reaction stages, facilitating both the interconversion of soluble polysulfides and the final deposition of solid Li2S. Specifically, the ZnSe-induced interface facilitates electron/ion transport and progressively strengthens polysulfide "catch" via strong chemisorption of Se sites. Meanwhile, the built-in internal electric field (BIEF) actively "converts" and accelerates reaction intermediates across multiple steps, which enables stage-matched conversion along the entire reaction pathway. Given these benefits, the optimized cathode delivers 1562 mAh g-1 at 0.1C and even upon 430 cycles at 1.0C, it demonstrates a minimal capacity loss of 0.067%. Employing sulfur content of 3.8 mg cm-2, a mere 0.096% capacity attenuation cycle-1 for 250 cycles at 0.2C. Advanced heterojunction design thus provides an innovative strategy to sequentially accelerate polysulfide stepwise conversion, paving the way for high-performance LSBs.

The conversion-based electrochemical energy storage mechanism of lithium-sulfur batteries (LSBs) involves lithium polysulfides (LiPSs) as the reaction intermediates. LiPSs dissolve in the electrolyte, leading to capacity losses and the shuttle effect. To tackle this, the physical confinement of sulfur and LiPSs using nitrogen-doped Ketjenblack and chemical anchoring via different crystal phases of ZrO2 is investigated. By combining theoretical analysis and experimental verification, a clear correlation between the electronic structure of ZrO2 crystal phases and their actual performance in LSBs is established. Compared to the cubic ZrO2 crystal phase, the monoclinic phase shows stronger binding energy with Li2S6 and a higher density of states near the Fermi level, which translates into more efficient redox kinetics and shuttle suppression as well as enhanced sulfur utilization in practical cells. Li-S coin cells assembled with an electrode containing monoclinic ZrO2 as the sulfur host provided a high initial discharge capacity of 1207 mAh g(-1) at 0.05 C, demonstrating stable long-term cycling at 2 C over 500 cycles with 84% capacity retention and a capacity loss of 0.03% per cycle. This demonstrates the promise of the monoclinic ZrO2 crystal phase for the chemical confinement of LiPSs in LSBs.

Potassium poly(heptazine imide) (K-PHI), an ionic carbon nitride, has gathered interest as functional material in energy conversion, in particular as photocatalyst. As a semiconductor, it lacks of electric conductivity. Paired with its low surface area, its potential is limited for electric and adsorption-based applications. This work reports the design of a PHI/carbon hybrid using micro- and mesoporous carbon as support in order to increase electric conductivity and the electrochemically-active surface area of K-PHI. By that, the specific surface area is increased from 9 m2 g-1 in bulk K-PHI up to 312 m2 g-1 when designing the mesoporous hybrid. Furthermore, transmission electron microscopy (TEM) images indicate a growth of K-PHI within the mesopores of the carbon, whereas the microporous hybrid exhibits K-PHI at the external surface. Both hybrids show enhanced capacitance up to 23 F g-1 compared to 2 F g-1 for bulk K-PHI. The mesoporous hybrid also shows enhanced capacitance retention at higher specific currents as the open mesopores enable faster ion diffusion combined with increased electric conductivity and shorter dielectric relaxation times. Overall, the design of K-PHI@carbon hybrids enables the study of electrochemical processes at the PHI surface without being limited by its low electric conductivity and low surface area.