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Room‐Temperature Rapid Synthesis of Crystalline Ag─C Coordinated MOFs for Highly Efficient Acidic CO ₂ Electroreduction

ABSTRACT The acidic CO 2 electroreduction reaction (eCO 2 RR) shows great promise in addressing carbonation issues encountered under neutral/alkaline conditions. However, it remains challenged by low selectivity arising from high proton availability, as well as catalyst degradation due to the corrosive and reductive nature of acidic media. In this work, we demonstrate a room‐temperature and rapid (< 5 min) synthesis of a novel crystalline Ag–C coordinated metal‐organic framework (TEPT‐AgC‐MOF) employing 4′‐(4‐ethynylphenyl)‐2,2′:6′,2″‐terpyridine as the ligand, enabling gram‐scale production. The incorporation of strongly covalent Ag–C bonds significantly enhances the structural stability of the catalyst under acidic conditions. Moreover, the triazine‐containing ligands in conjunction with a modulated electronic structure collectively enhance CO 2 adsorption, activation, and reduction efficiency. The resulting catalyst delivers outstanding eCO 2 RR performance in acid, achieving a CO Faradaic efficiency of 94.5%, a partial current density of 417.5 mA·cm −2 , and a turnover frequency (TOF) of 7357 h −1 , surpassing those of most reported Ag‐based acidic catalysts. Notably, this study not only establishes a facile route for synthesizing Ag‐MOFs, but also constitutes the first investigation into crystalline Ag–C coordinated MOFs as electrocatalysts for the acidic eCO 2 RR.

A Universal Fenton‐Like Strategy for Selective Generation of ¹ O ₂ in Mixed Industrial Wastewater Treatment and Green Chemical Synthesis

ABSTRACT Sustained and selective generation of singlet oxygen ( 1 O 2 ) in Fenton‐like catalytic systems is highly desirable for diverse applications, from freshwater resource management to green chemical synthesis. Despite advances in advanced oxidation processes, there remains a lack of generalizable methods that reliably modulate 1 O 2 selectivity. Here, we propose a descriptor‐assisted coordination modulation strategy, in which machine‐learning analysis identifies the d‐band center as an important electronic descriptor associated with 1 O 2 selectivity. Through N‐coordination modulation, the CoN 5 catalyst exhibited near‐complete 1 O 2 selectivity among the quantified reactive oxygen species (ROS) with a steady‐state concentration of 394 µM, outperforming recent reports. As an internal‐circulation pre‐oxidation module, the CoN 5 /peroxymonosulfate (CoN 5 /PMS) system continuously raised wastewater biochemical oxygen demand/chemical oxygen demand (BOD/COD) to above 0.5 over 192 h, increased bioavailable dissolved organic matter (DOM), and showed high microbiome compatibility, evidenced by reduced Vibrio fischeri inhibition and microbial diversity ordination clustering near the background with greater shared‐taxa overlap. This system also enabled selective thioanisole oxidation, achieving 90.6% conversion and 99.5% selectivity, with green synthesis potential demonstrated in a three‐chamber continuous single‐pass reactor. These results establish a generalizable coordination principle for steering ROS pathways and provide a deployable, low‐ecological‐risk route for both mixed wastewater treatment and green chemical synthesis.

Ion Bridging Enables Dual‐Interface Engineering for High Capacity and Long Cycling Aqueous Zinc–Sulfur Battery

ABSTRACT Aqueous Zn–S batteries (AZSBs) have garnered significant attention owing to their high energy density and low cost. However, their practical application is hindered by the limited electrochemical reversibility of sulfur cathode and the interfacial instability of zinc anode. Here, we developed a functionalized co‐solvent electrolyte incorporating aprotic polar tetramethylurea (TMU) and potassium iodide (KI) as synergistic additives, where TMU regulates the Zn 2+ coordination environment and cooperates with iodide species to construct an electrolyte‐derived, interface‐confined, and coordination‐mediated dynamic ion bridge pathway. This pathway couples TMU‐regulated Zn 2+ transport with I 3 − /I − ‐mediated charge transfer at the sulfur cathode interface, thereby reducing the kinetic barriers for Zn 2+ transport and ZnS conversion. Meanwhile, the TMU/KI‐regulated interfacial environment homogenizes Zn 2+ flux at the anode, promotes uniform Zn plating/stripping, and suppresses parasitic reactions. Through the synergistic regulation of the ion bridge, the AZSB delivers a high specific capacity of 759 mAh g −1 at 5 A g −1 and maintains over 71.2% capacity retention after 1000 cycles. This work proposes a promising electrolyte design strategy for energetic AZSBs via synergistic regulation, offering a promising route toward next‐generation sustainable energy storage systems.

Sebastian Clementson

Stereoselective Synthesis of Aminals Through Enzyme‐Catalyzed Intermolecular C(sp ³ )‐H Amidation of Azacycles

ABSTRACT Stereogenic aminals are widespread in natural products, pharmaceuticals, and biologically active compounds, including important classes of antibiotics. Methodologies for asymmetric synthesis of aminals are therefore highly desirable, yet they remain scarce and mostly rely on C─N bond formation at functionalized carbon centers such as carbonyls. Here we report the development of a strategy for asymmetric synthesis of aminals via direct, stereoselective C(sp 3 )–H functionalization of cyclic amines via an enzyme‐catalyzed intermolecular nitrene transfer reaction with dioxazolones. Using engineered variants of thermophilic cytochrome P450 (CYP119) from Sulfolobus solfataricus as catalysts, this approach enables the synthesis of a diverse set of indoline‐based aminals in good to high yields, excellent regio‐ and chemoselectivity, and with enantioselectivity up to >99% ee . This methodology could be further extended to pyrrolidines, piperidines, or morpholines as well as different dioxazolone reagents, yielding a diverse range of enantioenriched aminal scaffolds. This work expands the scope of abiological intermolecular C(sp 3 )–H amination reactions accessible through biocatalysis and provides a convenient, new route to the synthesis of enantioenriched aminal compounds.

Reflex Charging for Anion‐Derived Solid Electrolyte Interphase Formation

ABSTRACT Lithium (Li) metal offers exceptional energy density but suffers from unstable interphases that lead to dendrite growth and poor reversibility. Because the interphase is established during the earliest stages of operation, controlling its formation is critical for stabilizing Li metal electrodes. Here, we demonstrate that a reflex charging strategy, in which short discharge pulses are introduced during charging, dynamically reprograms the interfacial environment. This approach sustains anion enrichment near the electrode surface and shifts Li + solvation from solvent‐dominated structures toward anion‐coordinated structures, thereby promoting the formation of an inorganic‐rich interphase. The resulting interphase reduces interfacial resistance and enables dense and uniform Li deposition. Consequently, the reflex charging‐based formation protocol exhibits markedly improved Li deposition/stripping reversibility, and greater resistance to degradation during cycling and calendar aging. In full cells paired with LiFePO 4 (LFP) cathodes, the system retains 73% capacity after 500 cycles, demonstrating practical performance benefits. These findings establish formation protocol as an effective operation‐driven lever for controlling interfacial chemistry, offering a practical route that complements conventional materials‐based strategies for stabilizing Li metal batteries (LMBs).

Domino Effect in Epimer Self‐Assembly Induces Diverse Hydrogel Properties for Biomedical Applications

ABSTRACT Precise regulation of small‐molecule self‐assembly remains a formidable challenge, as subtle structural variations can trigger profound reprogramming of supramolecular architectures. Herein, we demonstrate that C18‐epimerization of glycyrrhizic acid (GA) acts as a molecular switch to modulate both its self‐assembly behavior and the properties of the resulting supramolecular hydrogels. Computational simulations and experimental analyses reveal that this epimer transition induces a “domino effect” that fundamentally rewrites the self‐assembly pathway, particularly by reshaping the intermolecular hydrogen‐bonding (H‐bond) network. Isoglycyrrhizic acid (IGA), the C18‐epimer of GA, forms a densely crosslinked fiber network through a distinct tetramer stacking mode, with significantly enhanced H‐bond interactions arising from altered electrostatic surface potential and molecular planarity. These structural differences yield hydrogels with enhanced injectability and viscosity, supporting the translational potential of IGA‐based hydrogel platforms. Furthermore, IGA co‐assembled with diverse therapeutic agents to form hydrogels that improved drug dispersibility and produced enhanced therapeutic effects in the evaluated preclinical models. This study elucidates the epimer‐governed cascade from molecular stereochemistry to macroscopic function and establishes a stereochemical strategy for engineering supramolecular biomaterials.

Bottlebrush Polyolefin Sulfones as Triggerable and Degradable Pressure‐Sensitive Adhesives

ABSTRACT The molecular architecture (topology) of bottlebrush polymers, featuring densely grafted side chains along a polymeric backbone, leads to unique physical properties, enabling their use as functional materials including elastomers and pressure‐sensitive adhesives (PSAs). Bottlebrush polymers can form additive‐free PSAs due to their architecture, but most are crosslinked materials that include all‐carbon backbones, have thermally unstable disulfide bonds, or do not reach the high molar masses needed for bottlebrush PSAs. Here, we applied the alternating free‐radical copolymerization of sulfur dioxide (SO 2 ) and norbornene‐based macromonomers in a grafting‐through approach to make bottlebrush polymers with number‐average molar masses exceeding 1100 kg/mol and backbone degrees of polymerization exceeding 900. These first examples of poly(olefin sulfone) bottlebrush polymers incorporated polyacrylate, polymethacrylate, polystyrene, and poly(lactic acid) side chains, all attached to a poly(norbornene‐ alt ‐SO 2 ) backbone. Under mild alkaline conditions, these very high molecular weight bottlebrush polymers degraded considerably within 10 min and completely within 4 h. Finally, a bottlebrush polymer synthesized using this approach behaved as a PSA with a peel strength of ∼1200 N/m, substantially higher than non‐degradable PSAs in commercial tapes. In sum, this work offers a versatile approach to synthesize triggerable and degradable bottlebrush polymer adhesives enabling end‐of‐life disposal following their intended applications.

Ionic Liquid Electrolytes for Extreme Temperature Conditions: Challenges and Perspective

ABSTRACT The increasing applications of electrochemical energy‐storage systems in transportation, aerospace, and grid applications impose stringent requirements on electrolytes capable of operating safely and efficiently across extreme temperatures. Conventional carbonate‐ or ether‐ based electrolytes suffer from performance degradation and severe safety hazards in extreme thermal environments. Ionic liquid electrolytes (ILEs), distinguished by their intrinsic nonflammability and remarkable resistance to temperature‐induced property fluctuations, are recognized as promising alternatives. Nonetheless, the development of wide‐temperature ILEs is constrained by their complex temperature‐dependent physicochemical behaviors and interfacial instabilities. In this review, the effects of temperature on the molecular configurations, physicochemical properties, and interfacial chemistry of ILEs are systematically elucidated. The challenges associated with ILEs operation under low‐ and high‐temperature conditions are subsequently delineated, with particular emphasis on recent advances in molecular design and co‐solvent strategies aimed at improving the wide‐temperature performance of ILEs. Furthermore, the interfacial chemistry and electrode compatibility of ILE‐based systems are examined to demonstrate their roles in dictating interphase stability and electrochemical durability. Integrating molecular‐level insights with macroscopic performance characteristics, this review presents a unified framework correlating the structure of ILEs with temperature‐dependent performance, providing valuable guidance for the rational design of next‐generation wide‐temperature ILEs toward high‐safety and high‐energy‐density rechargeable batteries.

Dyotropic Rearrangement of Hypervalent Iodine Species: Migrative Heterofunctionalization of Quaternary Carbons

ABSTRACT Phenonium intermediates are almost universally invoked to account for 1,2‐aryl migration processes in reactions that exploit in situ‐generated hypervalent iodine(III) leaving groups. Here, we demonstrate that such transformations can instead proceed through a previously unrecognized 1,2‐C/I(III) dyotropic rearrangement, which represents a fundamentally different mechanistic manifold in iodine(III) chemistry. Treatment of ethyl 2‐alkyl‐2‐aryl‐3‐iodopropanoates with Selectfluor and Py·9HF enables migratory aryl fluorination across a C(sp 3 )─C(sp 3 ) bond, installing fluorine regioselectively at the ester Cα position. The same dyotropic logic extends to migratory acyloxy arylation and alkoxy arylation reactions using hypervalent iodine reagents in combination with carboxylic acids or alcohols, respectively, and proceeds with inversion of absolute configuration at the Cα stereocenter. Although a phenonium intermediate is well‐established for many systems, this study demonstrates that a dyotropic rearrangement pathway can be energetically favored, offering a distinct rationale for the observed reaction outcome.

Pre‐Crosslinking via MOFs With Coordinatively Unsaturated Metal Sites for Fabricating Macroporous Hydrogels Toward Efficient Atmospheric Water Harvesting

ABSTRACT Freshwater scarcity is a global crisis, and sorbent‐based atmospheric water harvesting (SAWH) offers location‐independent water supply, yet developing fast‐kinetic adsorbents remains challenging. In this study, we report an MOF pre‐crosslinking strategy using metal–organic frameworks (MOFs) with unsaturated metal sites to prepare macroporous hydrogels. This strategy alleviates slow water diffusion induced by dense polymer chain stacking in traditional hydrogels. The obtained MOF pre‐crosslinked macroporous hydrogels (MPMHs) use MOF particles as cross‐linking nodes to construct interconnected macroporous networks, whose hydrophilic nanochannels facilitate rapid water transport inside cross‐linking domains. Compared with conventional hygroscopic salt hydrogel composites (HSHCs), MPMMHs exhibit greatly improved sorption–desorption kinetics and superior SAWH performance. MPMH‐101 attains 96% of its saturated water uptake (0.83 g g −1 ) within 30 min at 25°C and 30% RH, desorbs 70% stored water within 20 min at 70°C, and retains stable performance over 50 cycles. It delivers a water yield of 14.50 g g −1 day −1 at 30% RH and 9.70 g g −1 day −1 in outdoor tests which is 2.4 times higher than that of HSHCs. Moreover, this strategy is versatile to various water stable MOFs (MOF‐808(Zr), UiO‐66(Zr)), and polymers low methoxyl pectin (LMP), providing a potential solution for designing next‐generation SAWH adsorbents.

Giant Compressed Mo Blue Wheel {Mo ₁₁₈ }: A Molecular Photothermal Agent for High‐Effective NIR‐II Chemo‐Photothermal Therapy

ABSTRACT The rational construction of well‐defined polyoxometalate (POM)‐based second near‐infrared (NIR‐II) molecular photothermal agents (PTAs) and the elucidation of their structure‐activity relationships are crucial, but remain unresolved. Herein, we report a decameric molybdenum blue (MB) wheel {Mo 118 }, comprising a {Mo 112 } wheel capped by two {(SO 4 )Mo 3 } units, where compression of the giant ring arises from {Mo 1 *} units and distinct coordination modes of corner‐sharing {Mo 2 } units. As a rare structurally well‐defined POM‐based molecular PTA that exhibit photothermal conversion performance under NIR‐II region, {Mo 118 } features extensive delocalization of 28 Mo 4 d electrons within its framework, which endows it with a photothermal conversion efficiency of 50.8%, substantially outperforming that of the classical MB‐based analogue {Mo 154 } PTA. Femtosecond transient absorption spectroscopy further elucidates that a more rapid non‐radiative relaxation process in {Mo 118 } underpins its enhanced photothermal performance. By encapsulating {Mo 118 } into a dual‐responsive hydrogel via electrostatic interactions, a biocompatible system was constructed that affords photothermal‐triggered chemo‐photothermal therapy, demonstrating potent antitumor activity against 4T1 tumors both in vitro and in vivo. This work not only provides critical insights into the relationship between the electronic structure of POMs and their photothermal properties, but also establishes a new paradigm for the rational design of next‐generation molecular cluster‐based PTAs.

Unlocking the Distance Effect on CO ₂ Electroreduction to Multi‐Carbon Products via Monolayer Model Catalysts

ABSTRACT The interaction between adjacent active sites significantly influences electrocatalytic performance, for example, CO 2 electroreduction (CO 2 RR), yet quantifying this effect experimentally remains challenging due to the difficulty in precisely controlling inter‐site distances. Here, we construct a monolayer model catalyst using Cu‐coordinated porphyrins with well‐defined Cu–N 4 sites on Au(111). The distance between Cu centers is regulated at the sub‐nanometer level by modifying molecular ligands and aggregation states, and is directly measured by scanning tunneling microscopy (STM). This adjustable spacing critically determines the selectivity toward multi‐carbon products in CO 2 RR. When Cu sites are spaced 0.98 nm apart,a Faradaic efficiency (FE) of 6.1% for C 2 H 4 is achieved. Increasing the inter‐distance of Cu sites to 1.50 nm dramatically reduces C 2 H 4 FE to 1.2%. At larger separations of 1.63 nm and 1.74 nm, C─C coupling is almost completely suppressed, and C 2 H 4 production becomes negligible. These results provide direct experimental evidence of the distance effect in CO 2 electroreduction, and precisely identify, for the first time, the distance between Cu sites capable of facilitating C─C coupling process. This study establishes a molecular‐level platform for probing fundamental mechanisms in electrocatalysis.

Structural Water‐Enabled Helicity Emergence From an Asymmetric Achiral Molecule

ABSTRACT Helical supramolecular architectures are ubiquitous in nature yet remain challenging to construct from asymmetric achiral molecules. Here, we demonstrate that structural water acts as a symmetry‐breaking and frustration‐generating element in artificial self‐assembly. Using an asymmetric achiral naphthalene derivative ( N1 ) as a model system, we show that trace water fundamentally redirects its assembly pathway. In the presence of structural water, N1 forms racemic P/M helical fibers, whereas only non‐helical aggregates are obtained under anhydrous conditions or with control molecules lacking sufficient hydrogen‐bonding capability. Single‐crystal x‐ray analysis reveals that each water molecule functions as a tetravalent hydrogen‐bonding node, bridging four N1 molecules into a nonplanar C 2 ‐symmetric tetramer. This water‐centered motif introduces geometric incompatibility with optimal π–π stacking, generating packing frustration that is relieved through hierarchical helical twisting. The hydrogen‐bonding network can be reversibly modulated by acid–base stimuli, enabling interconversion between helical and non‐helical morphologies. Moreover, the resulting helices can be biased into homochiral states by chiral aromatic amino acids, revealing a water‐gated chirality transfer mechanism that is absent under anhydrous conditions. This work extends design principles for supramolecular helicity beyond conventional symmetric monomers and highlights the role of structural water in controlling complex self‐assembly pathways.

Component Self‐Initiated Photopolymerization for Gel Polymer Electrolytes in Zinc–Air Batteries

ABSTRACT Flexible zinc–air batteries (FZABs) require gel polymer electrolytes (GPEs) to ensure ionic transport, interfacial stability, and mechanical flexibility, yet their development is limited by trade‐offs among mechanical robustness, low‐temperature tolerance, and fabrication efficiency. Herein, a component self‐initiated photopolymerization strategy is developed to achieve rapid gelation within minutes under visible‐light irradiation without external initiators, providing an efficient route for fabricating high‐performance GPEs. Within a proton‐rich microenvironment, sodium citrate (SC) undergoes proton‐coupled electron transfer to generate radicals that initiate the copolymerization of vinyl monomers within a sodium alginate (SA) matrix, forming a double‐network hydrogel (AAS x ‐SA). Additionally, SC induces network densification via the Hofmeister effect and modulates electrochemical properties, resulting in mechanically robust, dendrite‐suppressing, and freeze‐resistant GPEs. Consequently, the optimized AAS25‐SA‐GPE exhibits an ionic conductivity of 109 mS·cm −1 at −40°C and a freezing point of −69.1°C, enabling stable operation of the AAS25‐SA‐based FZAB for over 4220 cycles at −40°C. This work establishes an electrolyte design strategy in which a single electrolyte component integrates photoinitiation, structural construction, and electrochemical regulation, transforming electrolyte additives into active building blocks.

Asymmetric Tellurium‐Bonding Catalysis for Mannich Reaction

ABSTRACT Chalcogen‐bonding catalysis has recently emerged as a powerful tool in organocatalysis. Nevertheless, its application in asymmetric transformations remains largely unexplored, primarily due to the scarcity of efficient chiral chalcogen‐bond donors. In this study, we report the design and synthesis of a series of chiral tellurium‐bonding catalysts based on an axially chiral 1,1′‐spirobiindane scaffold. Taking advantage of the highly directional and strongly polarizable tellurium‐centered donors along with a well‐defined C 2 ‐symmetric chiral environment, these catalysts enable cooperative bifunctional activation of substrates. Under optimized conditions, the asymmetric Mannich reaction of isatin imines with dicyanoolefins proceeds smoothly to afford a broad range of products in good to excellent yields with high enantioselectivities. Mechanistic studies support a dual chalcogen‐bonding activation mode involving cooperative interactions between the two tellurium centers and the isatin imine substrate. This work constitutes a seminal contribution to asymmetric catalysis enabled by chalcogen bonding and offers a new platform for the development of chiral tellurium‐bonding catalysts and related enantioselective transformations.

Allosterically Controlled Capture of Mutually Repulsive Guests With Positive Cooperativity and Ultrahigh Affinity

ABSTRACT A hexacationic cage incorporating three urea units can encapsulate two mutually repulsive anions in close proximity through a combination of hydrogen bonding and electrostatic interactions. This leads to exceptionally high binding affinities, with a K 1 × K 2 value of approximately 10 20 M ‒2 in MeCN‐ d 3 , for pairs of Cl ‒ or F ‒ anions. In its unbound state, the cage adopts a collapsed conformation stabilized by intramolecular interactions. These interactions are disrupted upon binding of the first anion guest, inducing an unfolded conformation that facilitates the binding of the second guest. Consequently, despite repulsion, the second Cl ‒ anion binds more strongly than the first by three orders of magnitude. This work presents a straightforward strategy for mimicking biological allosteric regulation and offers insights into the underlying physicochemical principles. The strong halide binding enables several applications. The cage can extract F ‒ from CaF 2 , suggesting a route to utilize fluorine from fluorspar for fluorochemical synthesis that bypasses the generation of hazardous HF. Furthermore, the cage can extract Cl ‒ or Br ‒ anions from organic halides, thereby stabilizing the corresponding carbocations and accelerating reactions involving these intermediates. In addition, the high affinity of the cage for halide anions released from fire suppressants provides for corrosion resistance.

Synthesis, Structure, and Photothermal Conversion of a Bowl‐Shaped Nanographene Containing Fused 5‐/7‐Ring Pairs

ABSTRACT Incorporation of non‐hexagonal topologies into bowl‐shaped nanographenes offers opportunities for tailoring their electronic properties and supramolecular behavior, however synthesis of such curved systems remains challenging. Herein, we report the facile synthesis of a bowl‐shaped nanographene ( TAT ) embedded with three circularly fused pentagon–heptagon (5/7) pairs via a three‐fold intramolecular Heck reaction. Its concave geometry is verified by nuclear magnetic resonance (NMR) spectroscopy, high resolution mass spectrometry, and x‐ray crystallography. Variable‐temperature 1 H NMR studies reveal a low bowl‐to‐bowl inversion barrier of 13.5 ± 1.3 kcal·mol −1 , enabling its fast dynamic motion even at room temperature. UV‐ vis absorption spectroscopy and cyclic voltammetry demonstrate a narrow energy gap, reflecting its highly delocalized π‐conjugation system. The concave geometry of TAT allows it to co‐assemble with fullerenes, forming a 2:1 complex with C 60 as confirmed by single‐crystal x‐ray diffraction analysis. Furthermore, femtosecond transient absorption spectroscopy reveals its ultrafast nonradiative excited‐state deactivation process. Benefiting from this photophysical behavior, water‐soluble nanoparticles of TAT encapsulated in an amphiphilic polymer achieve a high photothermal conversion efficiency of 41%. This work establishes a bottom‐up strategy for synthesizing an unprecedented bowl‐shaped nanographene and provides insights into its intrinsic optoelectronic, supramolecular properties, and photothermal conversion potentials.

Degradable Alternating Copolymers With Strained Cyclobutane Backbones via Photocontrolled RAFT Polymerization

ABSTRACT In this study, we report a reversible addition‐fragmentation chain transfer (RAFT) alternating copolymerization of 1,3‐disubstituted bicyclo[1.1.0]butanes (BCBs) with maleimides, maleic anhydride, or bio‐based fumarate derivatives, affording a class of well‐defined copolymers with strained cyclobutane backbones. Under visible‐light irradiation, a chain transfer agent (CTA)‐mediated photoiniferter process delivers BCB‐derived copolymers with a high degree of alternation, tunable molecular weights, and excellent end‐group fidelity. Our design leverages electronically and sterically tuned BCB monomers bearing an aryl substituent at one bridgehead and an electron‐withdrawing group at the other, facilitating precise control over radical reactivity and selective cross‐propagation. The resulting polymers exhibit high thermal stability with decomposition temperature up to 429°C, yet undergo highly efficient degradation under mechanical stimulation.

Regulating Solvation Chemistry via Strongly Coordinating Anion and Weakly Solvating Cosolvent for Low‐Temperature Sodium Metal Batteries

ABSTRACT Sodium metal batteries (SMBs) hold great promise for next‐generation energy storage systems due to their abundant sodium resources, high theoretical specific capacity, and low redox potential. However, they suffer from rapid capacity degradation at low operating temperatures, which inevitably hinders their practical application. In this work, we employ a strongly coordinating anion and a weakly solvating cosolvent to fabricate anion‐rich and varied solvation structures, aiming to enhance the low‐temperature electrochemical performance of SMBs. This unique solvation configuration efficiently reduces the Na + desolvation energy barrier, alleviates concentration polarization, accelerates liquid‐phase ion transport, and facilitates the in‐situ formation of a stable, highly ion‐conductive electrode‐electrolyte interphase. Benefiting from the synergistic regulation of interfacial stability and ion transport kinetics, dendrite‐free sodium deposition is achieved at −20°C, enabling stable cycling for over 500 h at 0.5 mA cm −2 and 0.5 mAh cm −2 . Additionally, the assembled SMBs exhibit excellent rate performance and cycling stability, delivering a high capacity retention of 70.54% and 68.28% after 1000 cycles at −20°C and −40°C, respectively. This work provides a novel perspective for the rational design of advanced electrolytes for high‐performance low‐temperature SMBs and lays a solid foundation for their practical application in cold environments.