Aqueous zinc-ion batteries (ZIBs) have received considerable attention for application in largescale energy storage. KV3O8 (KVO), a promising cathode material of ZIBs, possesses ion-diffusion-favorable robust and layered structure, but suffers from moderate electronic conductivity and sluggish Zn2+ diffusion, even worse in a low temperature. In this study, Zn2+ diffusion and electronic conductivity are boosted in KVO via polypyrrole preintercalation and accompanied oxygen vacancies, resulting much improved capacities and cycling stability both at room temperature and -25 degrees C. Further studies reveal that low-temperature Zn2+ motion is coupled with phonons and accelerated by phonon modulation. The coupling between Zn2+ and phonon provides a fundamental and deep understanding of ion motion in cathodes under low-temperature conditions.

Atomic-scale orchestration of multi-component interfaces is fundamental for mastering complex electrochemical conversions. Herein, we report a strained metal nanoisland epitaxy strategy to construct boron-doped Ag-Co core-island heterostructures on carbon nanofibers (IS-Ag/Co(B)/CNFs), specifically addressing the kinetic mismatch between initial reactant activation and subsequent protonation. Geometric confinement enables the coherent epitaxial growth of Ag domains on Co(111) surfaces, evolving from atomically layers to discrete nanoislands. This tandem architecture exhibits exceptional electrocatalytic nitrate reduction (NO3RR) performance, delivering high NH3 Faradaic efficiency of 96.3% and yield rate of 12.61 mg h- 1 mgcat- 1. In situ spectroscopy and theoretical calculations unveil a relay catalysis mechanism: the epitaxial Ag nano-islands initiate nitrate activation, while the underlying Co core functions as a high-flux proton reservoir to accelerate the subsequent hydrogenation of nitrogenous intermediates. Interstitial B-doping acts as an electronic modulator, reconfiguring interfacial orbital hybridization to optimize the adsorption energetics of hydrogenated intermediates while rigorously suppressing the competitive hydrogen evolution reaction. The practical utility is further validated by a Zn-NO3 - battery, achieving a stable open circuit voltage of 1.37 V and a peak power density of 2.02 mW cm- 2 alongside pollutant remediation. This work provides a versatile paradigm for programmable multi-component interfaces design, offering fundamental insights into orchestrating complex multi-proton/electron energy conversion processes.

ABSTRACT Electrochemical nitrate reduction to ammonia (NO 3 RR) is a promising pathway for nitrogen recycling but remains hindered by complex multistep kinetics and severe competition from the hydrogen evolution reaction. Coupling NO 3 RR with the sulfide oxidation reaction (SOR) offers an energy‐efficient alternative by simultaneously enabling dual‐pollutant remediation with value‐added products. Herein, we report an in situ exsolution strategy to construct a tandem electrocatalyst composed of exsolved Ag nano‐islands (NIs) anchored on a high‐entropy perovskite oxide matrix (Ag‐LaSrAgFeCoO x ). The structural complexity and abundant oxygen vacancies (O v ) of the LaSrAgFeCoO x synergistically interact with the exsolved Ag NIs, creating spatially and functionally distinct active sites. As a result, the Ag‐LaSrAgFeCoO x catalyst achieves high NH 4 + Faradaic efficiency of 97.6% and yield rate of 0.35 mmol h– 1 cm −2 . In situ characterization and theoretical calculations reveal a relay catalytic mechanism in which Ag sites of Ag NIs preferentially activate NO 3 – , while O v ‐rich LaSrAgFeCoO x promotes intermediates hydrogenation and NH 3 desorption, alongside efficient hydrogen supply. Moreover, the bifunctional Ag‐LaSrAgFeCoO x enables energy‐efficient NO 3 RR||SOR coupling, delivering a positive open‐circuit potential of 557 mV and stable co‐production of ammonia and sulfur. This work highlights high‐entropy materials as a powerful platform for tandem electrocatalysis in complex coupled reactions.

Lithium-rich layered oxides have gained considerable attention as cathode materials for lithium-ion batteries due to their high energy density. However, their insufficient structural stability results in rapid capacity fading and low initial Coulombic efficiency, hindering practical applications. In this study, we successfully synthesized medium-entropy Li1.2Ni0.13Co0.13Mn0.54O2 (LMNCO) through co-doping with Mg, Al, and La. The optimized Li1.2Ni0.12Co0.12Mn0.53Mg0.01Al0.01La0.01O2 exhibited outstanding electrochemical performance, including a high initial reversible capacity of 272 mAh g-1, an initial Coulombic efficiency of 82.2 %, and a capacity retention of 83 % after 100 cycles. These improvements can be attributed to the microstructural advantages, including optimized lattice parameters, enhanced lattice oxygen stability, and strengthened transition metal-oxygen bonds. Density functional theory (DFT) calculations further confirmed that Mg, Al, and La co-doping increased the adsorption energy (-3.12 eV) and the number of transferred electrons (0.87 e) compared with samples doped with each element individually. Meanwhile, the p-band center energy level of oxygen at the lithium adsorption site increased, further verifying that medium entropy facilitated the enhancement of electrochemical performance. The co-doping method suggests a promising strategy to develop cathode materials with enhanced capacity and stability, designed for the next generation of lithium-ion batteries.

The performance of lithium metal batteries （LMBs） is greatly hampered by the unstable solid electrolyte interphase （SEI） and uncontrollable growth of Li dendrites.To address this question,we developed a weak polar additive strategy to develop stable and dendrite-free electrolyte for LMBs.In this paper,the effects of additives on the Li + solvation kinetics and the electrode-electrolyte interphases （EEI） formation are discussed.The function of synergistically boosting the superior Li + kinetics and alleviating solvent decomposition on the electrodes is confirmed.From the thermodynamic view,the exothermic process of defluorination reaction for 3,5-difluoropyridine （3,5-DFPy） results in the formation of LiF-rich SEI layer for promoting the uniform Li nucleation and deposition.From the dynamic view,the weakened Li + solvation structure induced by weak polar 3,5-DFPy contributes to better Li + kinetics through the easier Li + desolvation.As expected,Li||Li cell with 1.0 wt% 3,5-DFPy exhibits 400 cycles at 1.0 mA cm -2 with a deposition capacity of 0.5 mAh cm -2 ,and the Li||LiNi 0.6 Mn 0.2 Co 0.2 O 2 batteries delivers the highly reversible capacity after 200 cycles.

Nanostructured high‐entropy alloys (nHEAs) are a prominent subclass of high‐entropy materials (HEMs). They exhibit a high specific surface area and vast morphological space enabled by their nanoscale dimensions, making them highly promising catalytic materials. Despite these merits, the nanostructure also introduces additional structural complexities and increases reconstruction during catalysis, which pose major challenges to their rational design. In this review, this inherent duality of nHEAs in catalysis is highlighted, and a comprehensive overview of recent advances aimed at addressing their structural complexities is provided. It is begun by elucidating the origins of these complexities, which mainly arise from the nearly infinite compositional possibilities, diverse atomic stacking configurations, and the intricate structures at the (sub)nanometer scale. Then, state‐of‐the‐art tools and methods are presented for managing these complexities and accelerating the discovery of next‐generation nHEAs catalysts, including high‐throughput synthesis and screening, first‐principle calculations, and machine learning. More importantly, emerging design principles are summarized that move beyond simple, trial‐and‐error compositional and configurational tuning, toward holistic and systematically integrated design strategies. This review delves into the intricate complexities of nHEAs and their corresponding strategies, aiming to provide valuable insights for their rational design in a variety of chemical transformations.

Regulating Zinc (Zn) nucleation and crystal growth on the anode surface is critical for reliable aqueous Zn metal batteries. However, achieving scalable and uniform surface modifications remains challenging. A Supercritical CO2-induced surface autogenous mineralization (SAM) strategy is introduced to fabricate a large-area, uniform, and crystalline Smithsonite autogenous regulating layer (ARL) on Zn foil. SAM enables in situ generation of H2CO3 and direct reactions with Zn under supercritical conditions, suppressing Zn2+ hydrolysis and inducing in situ mineralization. The ARL well-defined facets provide zincophilic sites, promoting single-crystal Zn nucleation and facilitating dense epitaxial deposition, thereby mitigating dendrites and enhancing cycling stability. The modified electrodes achieve over 1200 h with 99.48% Coulombic efficiency in SZn-4||Cu cells, over 3500 h in symmetrical cells, and over 8000 cycles in full cells at high current densities. This scalable SAM route offers a robust platform for high-performance, long-life Zn anodes in next-generation aqueous energy storage.

Poor reversibility of the Li anode and uncontrolled Li dendrite growth lead to the low Coulombic efficiency and serious security risks, which hinder the practical application of lithium (Li) metal batteries. Herein, we report an artificial solid electrolyte interphase (SEI) strategy for repressing Li dendrite growth and facilitating uniform Li deposition. The N-vinyl carbazole (NVK) was polymerized on the Li anode surface to form artificial SEI film. Such SEI film generates highly Li+ conductive lithium nitride (Li3N) to boost uniform Li+ flux and then facilitates uniform Li deposition on the Li anode. Therefore, the Li||Li symmetric cells showed excellent cycling performance with 350 cycles at 1.0 mA/cm2. Meanwhile, the Li||LiNi0.6Co0.2Mn0.2O2 (NCM622) batteries also achieved a higher cycling performance with a capacity retention of 87.5% after 150 cycles. This work provides a simple and effective strategy to solve the problem of dendrites in the Li metal battery.

ZrO2 aerogels are renowned for their exceptional stability and high positive charge, positioning them as promising candidates for various applications. However, the inherent frangibility and contractibility of ZrO2 aerogels pose significant challenges in processing and drying intactly. In this study, we introduce a novel approach to fabricate 3D-printed ZrO2-based aerogels through electrostatic attraction-assisted cogelation process, utilizing a silica reinforcement and rheological adjustment strategy. Under the dispersion and coordination effects of a silica sol with opposite charges, crack-free 3D-printed ZrO2-based aerogels were successfully prepared. These 3D-printed samples exhibit a low filament density of 221 mg cm-3 and an impressive specific surface area of up to 535.6 m2 g-1, showcasing superior performance in high-temperature insulation (withstanding temperature up to 1300 °C) and phosphate adsorption (with an adsorption capacity reaching 88.78 mg g-1). It is revealed that incorporated SiO2 is uniformly dispersed even at the primary structure level, forming a homogeneous hybrid skeleton. The zeta-potential results indicate that the uniform dispersion is due to the electrostatic attraction between positively charged ZrO2 sol and negatively charged SiO2 sol during the cogelation process. This innovative strategy paves the way for the development of ceramic-based inks suitable for 3D printing applications.

Phosphorus removal is a key technology to avoid water eutrophication. However, due to the relatively weak activity of phosphorous compounds, it is still a challenge to recycle them efficiently. In this paper, a 3D-printed acetylacetone-coordinating one-pot sol–gel strategy was proposed to prepare hybrid zirconia hydrogels with relatively high zeta potential (positive even when pH value reaches 8.0), high specific surface area (272.66 m2 g−1) and loose pore structure (average pore size is 5.97 nm). The adsorption experimental results showed that zirconia hydrogels had excellent phosphate adsorption performance, and the maximum adsorption capacity was 209.64 mg g−1. The most valuable thing was that the hydrogels still maintained a very high adsorption capacity (142.00 mg g−1) in a neutral environment. Zirconia hybrid hydrogel has higher surface potential (13.5 mV, pH = 6) and larger mesoporous structure (most probable pore size = 7.3 nm) than zirconia nanoparticles (5 mV, pH = 6; most probable pore size = 3.5 nm), which are beneficial to mass transfer, adsorption ability, and ultimately, excellent adsorption performance. Surprisingly, the zirconium-based hydrogel can realize 3D printing through ink direct writing technology, which endowed the block hydrogels with stable and macroscopical structure. The zirconia-based hydrogels constructed by 3D printing had a faster phosphate adsorption rate than the undesigned block hydrogels, and they were easier to recover than powdered adsorbents. The sol–gel and 3D printing strategy in this paper may provide a new idea for the optimal design of phosphate adsorbent for direct water treatment.

Highly stretchable porous materials are promising for flexible electronics but their fabrication is a great challenge. Herein, several kinds of highly stretchable conductive porous elastomers with low or negative Poisson’s ratios are achieved by uniaxial, biaxial, and triaxial hot-pressing strategies. The reduced graphene oxide/polymer nanocomposite elastomers with folded porous structures obtained by uniaxial hot pressing exhibit high stretchability up to 1200% strain. Furthermore, the meta-elastomers with reentrant porous structures combining high biaxial (or triaxial) stretchability and negative Poisson’s ratios are achieved by biaxial (or triaxial) hot pressing. The resulting elastomer-based wearable strain sensors exhibit an ultrawide response range (0-1200%). The materials can be applied for smart thermal management and electromagnetic interference shielding, which are achieved by regulating the porous microstructures via stretching. This work provides a versatile strategy to highly stretchable and negative-Poisson-ratio porous materials with promising features for various applications such as flexible electronics, thermal management, electromagnetic shielding, and energy storage.

Single-atom catalysts (SACs) have been widely utilized in lithium-sulfur (Li-S) batteries. However, their sluggish reaction kinetics and serious shuttling effects remain major challenges. Current research on SACs focuses on adjusting their coordination structure to bolster the adsorption and conversion of polysulfides while overlooking their enhancement through modulation of the electronic structure of the metal centers. This study proposes a novel approach for synthesizing nitrogen-doped Co-SACs (Co-SAC@NC). Theoretical calculations and experimental results indicate that nitrogen doping leads to a high Fermi energy level within Co-SAC@NC, signifying an elevated average energy of the electrons. This elevation results in significant splitting and lifting of degeneracy among d-orbitals in Co metal, which ultimately leads to a high-spin configuration. This configuration enhances the orbital interactions between the polysulfides and the catalyst, causing a decrease in the energy barrier and fast conversion from polysulfides to lithium sulfide. Thus, it improves the polysulfide kinetics. As a result, the batteries with the Co-SAC@NC modified separator exhibit a remarkable initial discharge capacity of 1465 mAh g−1 at 0.1C and excellent rate performance (736 mAh g−1 at 4C), outperforming most Co-SAC-based Li-S batteries.

MXenes, a new family of two-dimensional transition metal carbides, nitrides and carbonitrides, have emerged as promising materials for electrical energy storage (EES) systems due to their superior properties, such as high electronic conductivity, excellent mechanical capability, and hydrophily. These properties of MXenes are closely related to their structure and surface functional groups, and directly decided and readily tailored by means of synthesis methods applied. The properties of MXenes have a determining effect on the electrochemical performance of EES systems. This review begins with the intrinsic connections between properties and crystal structure, chemical composition and surface chemistry of MXenes as background. Then, the effects of latest synthesis on MXenes’ properties are systematically scrutinized, including the effects of precursors, processing parameters, the etching, delaminating, and compositing strategies of MXenes. Further focus is turned to the state-of-the-art progress of MXenes and their composites acting as cathodes, anodes, current collectors, electrolyte additives, and conductive binder in supercapacitors, monovalent (Li+, Na+, K+, and halogen anion) ion batteries, and multivalent (Zn2+, Mg2+, Ca2+, and Al3+) ion batteries. The synthesis-property-application relationships in MXenes for desired EES devices are highlighted. Finally, the critical challenges and perspectives are discussed for the future development of MXenes in advanced supercapacitors and rechargeable batteries.

The key to fully realizing the potential of high-entropy alloys (HEAs) lies in balancing their inherent local chemical disordering with the long-range ordering required for electrochemical applications. Herein, we synthesized a distinctive L1 0 -(PtIr)(FeMoBi) high-entropy intermetallics (HEIs) exhibiting nanoscale long-range order and atomic scale short-range disorder via a lattice compensation strategy to mitigate the entropy reduction tendency. The (PtIr)(FeMoBi) catalyst exhibited remarkable activity and selectivity of glycollic acid (GA) production via electrocatalytic waste polymer-derived ethylene glycol oxidation reaction (EGOR). With a mass activity of 5.2 A mg Pt −1 and a Faradaic efficiency (FE) for GA of 95 %, it outperformed most previously reported electrocatalysts for selective GA production. The lattice-compensation effect promotes the homogeneity of Pt and Fe actives sites, facilitating co-adsorption of EG and OH and reducing the energy barriers for dehydrogenation and OH-combination processes. This approach effectively avoids the formation of low-active sites commonly encountered in HEA solid solutions, offering a promising avenue for exploring the complex interplay between catalytic activity and HEI structures.

Sodium-ion batteries (SIBs) are attractive for energy storage applications owning to the abundant raw resources and low cost, supplementing the pervasive lithium-ion batteries, particularly for the large scale and stationary applications. Among various active materials, 2D MXenes are considered as promising electrode materials for SIBs due to their excellent physical/chemical characteristics, such as high conductivity, various chemical compositions, tunable structure, and abundant surface functional groups. In this review, the structure and properties of MXenes are initially introduced and elaborated, followed by discussion of influence factors on electrochemical properties. The state-of-the-art progress in the design and synthesis of MXenes and their composites, together with their properties and electrochemical performance of SIBs are then comprehensively summarized. The corresponding Na+ storage mechanisms are also analyzed to establish connections between synthesis methods, material properties, and device's performance. Finally, a summary and perspectives are presented for possible further development of MXene-based SIBs.

The manipulation of surface catalytic sites has rarely been explored for metal borides, and the subsurface effects on the electrocatalytic activity of the nitrogen reduction reaction (NRR) remain unknown. Herein, this work develops a core-shell nanoparticle catalyst with a Pd core that ensures high electron transfer rates and an Pd16B3 atomical shell that possess tunable active sites for regulating the NRR. The atomic structural evolution from Pd to Pd16B3 is investigated by precisely controlling the B atom diffusion, molecular rearrangement, and d-sp orbital hybridization. Pd/Pd16B3 core-shell nanocrystals exhibit an exceptional NRR performance with a high NH3 Faradaic efficiency of 30.8%, which is superior to those of pristine Pd (1.2%) and B-doped Pd (4.8%) under identical conditions, and a yield rate of 0.81 mu mol h(-1) cm(-2). This work discovers that the Pd16B3 shell could promote the NRR selectivity by separating the separating the hydrogen evolution reaction proceeded on hole sites and NRR proceeded on bridge sites, and the Pd core could provide the excellent conductivity to Pd16B3 shell through regulated electron interactions. Consequently, the controlled chemical ordering of palladium boride on palladium surfaces provides insight into the synthesis of advanced NRR electrocatalysts.

Zinc-ion batteries (ZIBs) show great promise for next-generation energy storage, but their performance at low temperatures is severely hindered by sluggish desolvation kinetics at cathode-electrolyte interface. To address this limitation, a zincophilic-hydrophobic poly(3,4-ethylenedioxythiophene) (PEDOT) modified layer is proposed on V5O12 center dot 6H(2)O cathode. Ab initio molecular dynamics simulations indicate that this modification strategy promotes Zn2+ adsorption and reduces the free energy for dissociating hydrated Zn2+ to form Zn2+ at the cathode-electrolyte interface, across the temperature of 280 to 240 K. As a result, this PEDOT-modified cathode exhibits significantly improved Zn2+ diffusion and desolvation kinetics, delivering superior rate performance with a remarkable capacity of 226.5 mAh g(-1) at 40 A g(-1). Notably, even at -30 degrees C, this cathode maintains a high capacity of 268.3 mA g(-1) at 0.2 A g(-1) and exhibits robust capacity retention (92.4%) over 1,000 cycles at 1 A g(-1). This approach markedly improves low-temperature capacity retention and operational efficiency, highlighting the potential of cathode-electrolyte interface engineering to advance zinc-ion batteries performance in cold environments.

While high-entropy alloy (HEA) catalysts seem to have the potential to break linear scaling relationships (LSRs) due to their structural complexity, the weighted averaging of properties among multiple principal components actually makes it challenging to diverge from the symmetry dependencies imposed by the LSRs. Herein, we develop a 'surface entropy reduction' method to induce the exsolution of a component with weak affinity for others, resulting in the formation of few-atom-layer metal (FL-M) on the surface of HEAs. These exsolved FL-M surpass the confines of the original configurational space of conventional HEAs, and collaborate with the HEA substrate, serving as geometrically separated active sites for multiple intermediates in a complex reaction. This FL-M-covered HEA shows an outstanding performance for electrocatalytic reduction of nitrate to ammonia (NH3) with a Faradaic efficiency of 92.7%, an NH3 yield rate of 2.45 mmol h-1 mgcat.-1, and high long-term stability (>200 h). Our work achieves the precise manipulation of atomic arrangement, thereby expanding both the chemical space occupied by known HEA catalysts and their potential application scenarios.

Zinc-ion hybrid capacitors (ZICs) are of interest for their optimal balance between power and energy density. Among the cathode materials, silicon is particularly attractive due to its abundance and potential compatibility with the microelectronics industry. However, silicon-based materials exhibit specific capacitances far below 100 mF cm-2 because of their inherently low electronic and ionic transport, making them less competitive than other nanomaterials such as carbon and MXenes. In this study, state-of-the-art silicon-based ZICs using Mg-doped porous silicon (PSi) derived from silica aerogels are constructed. The improved electronic conductivity achieved by Mg doping, combined with enhanced ion diffusion promoted by the porous structure, results in excellent electrochemical properties of the ZIC. Consequently, the prepared ZIC exhibits a specific capacitance of 106.1 mF cm-2 at 0.2 mA cm-2 with remarkable cyclic stability (92% retention after 20 000 cycles). Additionally, the pouch ZICs using gel electrolytes demonstrate good rate capability and a long lifespan, indicating significant potential for practical applications. These results underscore the potential of heteroatom-doped PSi as a cathode for ZICs. Magnesium-doped porous silicon (PSi) is achieved by magnesiothermic reduction of SiO2 aerogels and utilized as a cathode for advanced aqueous silicon-based zinc-ion hybrid capacitors (ZICs). The ZICs exhibit remarkable specific capacitance due to magnesium doping and hierarchical porous architecture. This strategy shows the potential of heteroatom-doped PSi as a cathode for ZICs.image