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Stimuli‐Responsive Triplet Emission and X‐Ray Scintillation via Reversible Structural Switching in Pyromellitic Diimide Cocrystals
ABSTRACT Smart stimuli‐responsive luminescent materials with programmable and reversible emission are highly desirable for intelligent imaging and information security. Stimuli‐responsive organic materials utilizing triplet excitons are particularly attractive owing to their pronounced sensitivity to solid‐state packing. However, crystallinity‐preserving reversible structural switching that enables simultaneous control over X‐ray‐excited luminescence (scintillation) remains largely unexplored. Herein, donor‐acceptor halogen‐bonded cocrystals were constructed using N , N ′‐bis(n‐butyl)pyromellitic diimide (Bu 2 PMDI) and 3,6‐dibromocarbazole (Br 2 Cz) or 3,6‐diiodocarbazole (I 2 Cz). The green cocrystal Bu 2 PMDI‐Br 2 Cz‐G exhibits room‐temperature phosphorescence (RTP) and bright radioluminescence, whereas its orange polymorph is nearly non‐emissive. In contrast, the I 2 Cz‐based cocrystal displays thermally activated delayed fluorescence (TADF), representing an alternative triplet exciton utilization pathway. Notably, mild organic‐vapor stimulation triggers reversible order‐to‐order polymorphic interconversion of Bu 2 PMDI‐Br 2 Cz, which reorganizes halogen‐bonding motifs and, thus achieves crystallinity‐retained “on/off” switching of radioluminescence. Benefiting from efficient triplet exciton utilization, Bu 2 PMDI‐Br 2 Cz‐G enables high‐resolution static X‐ray imaging (37 lp mm −1 ) and real‐time dynamic imaging (2 K, 60 fps) with negligible afterglow. Furthermore, the reversible solvent‐triggered luminescence switching facilitates rewritable multimodal information encryption by integrating photoluminescence and radioluminescence as orthogonal readout channels. This work demonstrates cocrystal engineering as a powerful strategy for reversibly programming triplet‐exciton emission and X‐ray scintillation via structural switching in organic solids.
Engineering of Artificial Antioxidase Enables Boosted Catalytic Activity in Inflammatory Bowel Disease Alleviation
ABSTRACT Developing artificial antioxidases represents a promising strategy for treatment of oxidative‐stress‐related disorders; however, their practical application is often hindered by insufficient catalytic activity. Here, we report a dual‐cobalt coordinated phthalocyanine carboxylate derivative (biCoPc) as an efficient artificial antioxidase with markedly enhanced reactive oxygen species scavenging capability for the alleviation of inflammatory bowel disease (IBD). Experimental studies combined with theoretical calculations reveal that the extended π‐conjugation and π‐electron delocalization within the dimeric phthalocyanine framework, together with the protonation‐deprotonation dynamics of peripheral carboxyl groups, synergistically promote a potential proton‐coupled electron transfer process at the dual‐cobalt active sites. This architecture accelerates electron transfer kinetics and creates a favorable catalytic microenvironment. Consequently, biCoPc exhibits high catalytic superoxide dismutase‐like and glutathione peroxidase‐like activities, along with robust stability under harsh conditions. Notably, biCoPc demonstrates pronounced anti‐inflammatory efficacy, efficiently alleviating IBD symptoms at both the cellular level and animal models. This work provides mechanistic insights into the rational design of high‐performance artificial enzymes and broadens their potential for biomedical applications.
Unlocking Durable High‐Power Zn‐Air Batteries: {Fe <sub>3</sub> O} Molecular Furnace‐Forged Dual‐Site Catalysts Enabling Synergistic Oxygen Reduction in Alkaline Media
ABSTRACT Atomic‐level precision metal‐oxo clusters serve as a unique bridge linking single atoms and nanoparticles. Their highly ordered, quasi‐molecular structure effectively promotes electron transfer and optimizes charge deposition kinetics, thereby significantly enhancing the catalytic activity and stability of electrochemical oxygen reduction reactions. Here, we constructed a single‐atom‐nanoparticle dual‐engine catalyst (Fe 3 C/Fe‐NC 1050 ) by in situ domain‐confined complexation of ZIF‐8(Zn) using {Fe 3 O} as a core metal‐oxo cluster. The unique flexible ligand‐carboxylate group of {Fe 3 O} clusters provide a protective barrier for the metal atoms distribution during pyrolysis, work in synergy with the ZIF‐8 framework to provide a conductive substrate. The precisely exposed Fe 3 C (110) crystal plane modulates the electronic structure of neighboring Fe‐N 4 active sites, thus reducing the adsorption energy of key step O 2 →*OOH and endowing the material with excellent methanol resistance and stability. Structural characterization and theoretical calculations reveal that the synergistic interaction between {Fe 3 O} clusters and the carbon substrate provides a stable conductive network and active sites, achieving a maximum power density of 249.0 mW cm −2 in alkaline zinc‐air batteries and demonstrates exceptionally long cycle life of 700 h at the current density of 2.0 mA cm −2 . This design provides crucial insights for the nanoengineering of metal‐oxo clusters and atomic‐scale design of catalysts.
Emergence of Chiral Defective Pores Through Chiral Linker Exchange in Nonchiral MOFs for Enantioselective Recognition
ABSTRACT Enantioselective recognition is vital for numerous chemical and biological applications, which, however, remains challenging due to the nearly indistinguishable physicochemical properties of enantiomers. In this study, we report a luminescent sensing strategy for enantioselective recognition based on metal‐organic frameworks (MOFs) constructed through chiral linker exchange, which simultaneously introduces chirality and defective sites into the frameworks. The resulting chiral defective MOFs exhibit confined nanopore environments, resulting in distinct luminescence responses toward enantiomers. A pair of enantiomeric MOFs was constructed, exhibiting opposite selective recognition performance toward R‐ and S‐substrates. The sensing behavior arises from the interplay of competitive absorption and electron transfer process, while disparities in binding affinities serve as the dominating factor dictating the enantioselectivity. Meanwhile, this system enables the quantitative detection of enantiomeric excess (ee) values in mixtures through differential luminescence responses. Due to its facile synthesis routes, selectivity, and ease of implementation, this strategy offers a practical approach for developing chiral luminescent sensing materials, while highlighting the significance of host‐guest interactions in sensing.
From P‐Type to Bipolar: A Quinone‐Core Engineering Strategy in D‐A‐D Organic Cathodes for Ultra‐Stable and High‐Energy Organic Lithium‐Ion Batteries
ABSTRACT In this study, we present a rational donor‐acceptor‐donor (D‐A‐D) molecular design strategy to develop high‐performance organic cathodes by enhancing the intramolecular charge transfer (ICT) effect. We designed and synthesized two organic molecules: 2,6‐bis(10H‐phenothiazin‐10‐yl)benzo[1,2‐d:4,5‐d’]diimidazole‐4,8‐dione (PTZBQ), featuring a strong quinone‐type acceptor core, and the control compound 2,6‐bis(10H‐phenothiazin‐10‐yl)benzo[1,2‐d:4,5‐d’]diimidazole (PTZTAB), without a quinone core. The strong push‐pull electronic structure of PTZBQ not only results in a significantly narrowed bandgap and improved electrode kinetics, but also allows the quinone core to contribute extra n‐type capacity, thereby remarkably boosting the electrode's specific capacity and reaction dynamics. Moreover, the extended π‐conjugation and D‐A‐D configuration‐induced polarity endow both small molecules with exceptional electrolyte dissolution resistance. Consequently, PTZBQ exhibits bipolar redox activity, delivering a high discharge potential of 3.05 V, a high specific capacity of 163.3 mAh g −1 at 0.1 A g −1 , an excellent rate capability (77.6% retention at 5 A g −1 ), and exceptional long‐term cycling stability with 89.4% retention after 5000 cycles at 1 A g −1 . DFT calculations and ex situ spectroscopy confirm that the unique D‐A‐D architecture possesses spatially separated n‐type and p‐type redox centers, facilitating the redox process. Our findings highlight that quinone‐core engineering enhances intramolecular charge transfer and represents a powerful approach for developing high‐performance cathode materials.
Atomic Coordination Engineering of MOF Nanostructures for CO <sub>2</sub> Electroreduction to High‐Value Multi‐Carbon Products at Industrial‐Level Current Density
ABSTRACT Metal–organic frameworks (MOFs) have shown great promise for electrochemical carbon dioxide (CO 2 ) reduction into value‐added chemicals/fuels, thereby supporting the balance of carbon‐neutral energy cycle. The multi‐carbon (C 2+ ) production on MOF electrocatalysts is of great significance but remains challenging due to inefficient C–C coupling. Here, we report the atomic coordination regulation of MOF nanostructures (Cu‐Trz‐Br) for efficient CO 2 electroreduction by rationally designing dual‐site Cu catalysts. The crystallographic structure of Cu‐Trz‐Br is determined by three‐dimensional electron diffraction and Rietveld refinement against high‐resolution powder X‐ray diffraction data, which feature unique mixed coordination modes of Cu–N 4 Br 2 and Cu–N 4 sites. In CO 2 electroreduction, Cu‐Trz‐Br demonstrates much enhanced selectivity toward C 2+ products compared to common counterparts with only Cu–N 4 sites, enabling efficient C 2+ production under industrial‐level current density. In situ studies and theoretical calculations reveal that the coordination regulation of Cu–N 4 Br 2 sites promotes CO 2 adsorption and activation, as well as effectively enhances local *CO availability near Cu‐Trz‐Br, thereby facilitating C–C coupling toward C 2+ products.
Charge‐Polarized Interfacial Engineering Enables Radical Management for 1000 h Electrosynthesis of <i>Para‐</i> Benzoquinone
ABSTRACT Radical‐mediated organic electrosynthesis frequently suffers from limited selectivity and catalytic instability, largely arising from uncontrolled radical coupling and overreaction. These challenges intensify under large‐current conditions, where accelerated radical generation promotes competing side reactions and undermines practical implementation. Here, we introduce a charge‐polarized interfacial engineering strategy to address these issues, demonstrated using a Cr 2 O 3 /Ru‐Fe 2 O 3 heterostructure to drive the selective electro‐oxidation of phenol to para‐ benzoquinone ( p‐ BQ). The polarized interface enforces a vertical adsorption configuration of phenoxy radicals, suppressing Langmuir−Hinshelwood polymerization while stabilizing high‐valent Ru oxidative centers and facilitating rapid desorption of p‐ BQ product. As a result, the catalyst achieves 1000 h of continuous p‐ BQ electrosynthesis at record steady‐state current densities above 40−50 mA cm −2 , delivering high product selectivity and parallel hydrogen production at 1.0 V in an asymmetric hybrid seawater electrolyzer. This work establishes interfacial radical management as an effective framework for efficient electrosynthesis of value‐added chemicals.
Ultra‐Thin and Highly Insulating Aromatic Monolayers by <i>N</i> ‐Heterocyclic Carbenes
ABSTRACT The efficiency of organic electronic devices relies on application of organic gate dielectric materials. Such organic films should exhibit high chemical/thermal stability, aromatic functionality compatible with organic semiconductors, and low gate leakage currents in combination with low thickness to reduce the operating voltage. An interesting class of materials for such applications are self‐assembled monolayers (SAMs) among which the N ‐heterocyclic carbenes (NHC) are known for their high chemical/thermal stability. The conductivity of NHC SAMs, however, has been sparsely explored and their electrical properties remain controversial. Here we report conductivity analysis for a well‐defined series of aromatic NHC SAMs. Our data show that all analyzed monolayers are highly insulating and in particular the shortest possible NHC of just ∼3.3 Å is by 5 orders of magnitude more insulating than standard insulators based on alkanethiolate SAM of the same length. Our calculations indicate the absence of destructive quantum interference (DQI) effect which has been considered responsible for suppression of conductivity in aromatic molecules. The suppression of SAMs conductivity just via selection of the imidazolium‐based bonding group is conceptually simpler opening possibility of using NHC SAMs as an ultra‐thin, and exceptionally insulating, aromatic monolayers for functionalization of the gate electrodes.
Engineering Pluripotent Stem Cells‐Derived Inner Ear Organoids With Enhanced Maturation and Reproducibility by Micro‐Topographical Cues
ABSTRACT Inner ear organoids (IEOs) derived from pluripotent stem cells (PSCs) provide a promising platform for modeling neurosensory disorders and hearing loss; however, conventional systems often exhibit substantial structural variability, incomplete maturation, and limited reproducibility due to insufficient control of early organoid morphogenesis. Here, we demonstrate that micro‐topographical cues applied during initial IEO formation enhance the development and functional maturation of PSC‐derived IEOs. This microengineering strategy introduces temporally defined microscale geometric confinement to regulate early cell‐cell and cell‐extracellular matrix (ECM) interactions, thereby promoting epithelial organization and developmental fidelity. Microengineered IEOs (M‐IEOs) exhibit improved reproducibility and neurosensory maturation, including increased hair cell‐like populations, stereocilia‐like structures and kinocilium‐like features exhibiting a characteristic (9 × 2) + 2 microtubule organization. Functionally, M‐IEOs exhibit enhanced electrophysiological responsiveness, supported by complementary transcriptomic and in situ analyses indicating activation of inner ear lineage maturation pathways. Furthermore, we demonstrate the versatility of M‐IEOs by integrating them with a microfluidic vascular system to model vascular‐epithelial interactions and inflammatory responses, highlighting its potential for disease modeling and pharmacological screening. Together, these findings establish transient micro‐topographical guidance as an instructive regulator of inner ear organoid development and provide a robust, vascular‐compatible platform for neurosensory research, disease modeling, and translational screening applications.
Thiophene‐Engineered Lipid II Recognition Enables Potent Membranolytic Eradication of MRSA
ABSTRACT Methicillin‐resistant Staphylococcus aureus (MRSA) remains a significant global health threat, necessitating the development of new antimicrobials. We report the rational design of a small molecule TPL(II)‐07, that combines multiple functional modules: (i) 2‐phenylthiophene for specific recognition and binding to lipid II, a key intermediate in peptidoglycan biosynthesis; (ii) an adamantane fragment with high interfacial permeability to destabilize lipid packing; (iii) a cationic lysine moiety to disperse biofilms; and (iv) a moderate aliphatic chain to disrupt membrane integrity. Among seven analogues, TPL(II)‐07 exhibited the highest potency, highlighting the synergistic contribution of each component. Mechanistic assays confirmed preferential binding of lipid II, bactericidal potency, biofilm dispersion, and the generation of reactive oxygen species, effective against both drug‐resistant (MIC 19 µM) and drug‐sensitive (MIC 9 µM) S. aureus strains. TPL(II)‐07 demonstrated excellent biocompatibility, with IC 50 > 50 mM in HEK‐293 and WI38 cells and negligible hemolytic activity. In addition, it suppressed key virulence traits, including hemolysin activity, biofilm formation, and staphyloxanthin production. Further, a borate‐functionalized guar gum hydrogel incorporating TPL(II)‐07 achieved effective infection control and enhanced wound repair in a murine excisional model, establishing thiophene‐based lipid II targeting as a versatile platform for next‐generation antimicrobials with dual antibacterial and wound‐healing potential.
Autocatalytic Eutectic Gel Electrolyte for Quasi‐Solid State Zn‐Ion Cells
ABSTRACT Hydrated eutectic electrolytes offer immense application potential for zinc‐ion batteries. However, the high reactivity between the electrodes and hydrated eutectic electrolytes causes dendrite growth and cathode dissolution owing to the unstable and adverse interface layer formation. Although gelation of the eutectic electrolyte can mitigate the reactivity, the traditional polymerization initiation strategy still leads to severe residual monomers and initiators. These highly chemically and electrochemically reactive residual monomers/initiators can further react with the electrodes, deteriorating the electrode interface and ultimately leading to battery performance degradation. Herein, we designed an initiator‐free acrylamide eutectogel electrolyte featuring autocatalysis, wherein polymerization is spontaneously driven by its own components, which reduces residual monomer and in situ converts residual acrylamide into a nitrogen‐containing protective interphase during cycling, thereby suppressing the hydrogen evolution reaction, harmful chlorinated by‐products, and cathode dissolution. As a result, the Zn||NaV 3 O 8 ·1.5H 2 O cells deliver a capacity of 172.7 mAh g −1 with 98.5% retention over 2450 cycles at 1.0 A g −1 , and can also cycle stably at −20°C and 65°C. This autocatalytic polymerization strategy holds great promise for other polymer monomers and Lewis acid salts, and may offer a scalable approach to developing long‐life quasi‐solid zinc batteries.
Selective Synthesis of [2]Rotaxane Orientational Isomers With Precisely Arranged Luminogens: Toward Orientation‐Dependent Emissions for Information Storage and Encryption
ABSTRACT Aiming at the precise synthesis of rotaxane orientational isomers and the further elucidation of attractive orientation effects, a novel steric hindrance‐controlled selective stopper exchange approach has been successfully developed. This method enables the facile and selective synthesis of six pairs of [2]rotaxane orientational isomers with precisely arranged luminogens, greatly enriching both the structural and functional diversity of such isomers. Notably, the resulting orientational isomers exhibit orientation‐dependent emission behaviors, particularly in wavelengths, photoluminescence quantum yields, and circularly polarized luminescence (CPL) performances, endowing them with great potential for information storage and encryption. This proof‐of‐concept study provides not only a practical and efficient strategy for the efficient synthesis of rotaxane orientational isomers, but also a novel platform for constructing chiral luminescent materials with desired properties for wide applications.
Holistic Inside‐Out Reconfiguration of Ni‐Rich Cathodes via a Thermally Self‐Driven Strategy for Exceptional Chemomechanical Stability
ABSTRACT Ni‐rich layered oxides (LiNi x Co y Mn 1− x − y O 2 , x ≥ 0.8) are indispensable for high‐energy‐density lithium‐ion batteries, yet they suffer from severe chemomechanical degradation driven by the synergy of internal microcracking and interfacial parasitic side reactions. Existing strategies inherently suffer from decoupled regulation of mechanical and chemical instabilities that fail to address these issues holistically. Here, we develop an inside‐out structural reconfiguration strategy driven by the thermal decomposition of nitrates, concurrently tailoring the core, bulk, and surface of NCM811 in a single calcination step. This reconstruction generates a stress‐buffering central pore architecture that effectively homogenizes anisotropic lattice strain and suppresses crack nucleation. Concurrently, the regulated Nd 3+ diffusion forms a coherent Nd 4 [LiNi]O 8 (NLNO) perovskite phase within the bulk lattice, creating a pinning effect that stabilizes the layered framework and enhances charge transport. Furthermore, excess Nd‐species evolve into a conformal NLNO surface coating, acting as a physical barrier and oxygen reservoir to resist electrolyte attack and oxygen evolution. The modified cathode delivers an exceptional capacity retention (95.7% after 200 cycles at 4.5 V) and exceptional rate capability (157.1 mAh g −1 at 5 C). Even under stringent conditions (4.6 V or 45°C), a superior retention of 87.8% is maintained after 200 cycles, demonstrating remarkable chemomechanical robustness.
Balancing Dimerization and Hydrogenation Kinetics by Stabilizing Cu <sup>+</sup> and Tightening H‐Bond Network for Electrocatalytic Acetylene Hydrodimerization
ABSTRACT The electrocatalytic hydrodimerization of acetylene (EHDA) offers a promising alternative to energy‐intensive naphtha steam cracking for producing 1,3‐butadiene but faces a formidable challenge due to kinetic imbalance between C–C coupling and hydrogenation. Herein, we balance the dimerization and hydrogenation kinetics of EHDA by stabilizing Cu + and tightening the hydrogen‐bond network over citrate anion grafted Cu 2 O catalysts (E‐CA/Cu 2 O). The X‐ray absorption fine structure, Cu LMM Auger spectrum, and theoretical simulations corroborate citrate anion modification induces electron transfer from Cu 2 O to citrate ions. This stabilizes the active Cu + sites under electrochemical reduction conditions and further lowers the C‐C coupling barrier of *C 2 H 2 and *C 2 H 3 to *C 4 H 5 . The in situ attenuated total reflection surface‐enhanced infrared spectroscopy confirms that the citrate anion also reconstructs the hydrogen‐bonding network and reduces the content of isolated water at the electrode‐electrolyte interface. The appropriate supply of active *H species effectively promotes the hydrogenation of *C 4 H 5 to form 1,3‐butadiene rather than competitive acetylene semihydrogenation. As a result, E‐CA/Cu 2 O catalyst achieves a Faradaic efficiency of 88.0% and a 1,3‐butadiene partial current density of 55 mA cm −2 , which is about 3‐fold higher than E‐Cu 2 O. This work will guide the rational design of high‐performance catalysts for regulating the kinetics of electrocatalytic acetylene hydrodimerization.
Multifunctional Conductive MXene Binders for Battery and Supercapacitor Electrodes
ABSTRACT Binders serve as a pivotal component in electrode fabrication as they can adhere active materials and conductive additives to the current collector. Nevertheless, the diversified development of electrochemical energy storage systems (ESSs) necessitates heightened functionality requirements for electrode binders, thereby motivating the exploration of a broad spectrum of binders tailored to fulfill various requirements. In recent years, two‐dimensional Ti 3 C 2 T x MXene has emerged as a promising binder candidate for electrode fabrication. Compared to traditional polymer binders, MXene offers a unique combination of properties highly beneficial for electrode fabrication, including metallic electrical conductivity, exceptional mechanical/adhesion strength, intrinsic flexibility, rich surface chemistry, and good electrochemical activity. These features collectively improve the electrochemical performance of the as‐fabricated electrodes, including capacity, rate capability, and cycling stability, across diverse ESSs. Herein, we present a comprehensive overview of recent advances in multifunctional MXene binder for electrode fabrication, particularly in combination with diverse active materials for ESSs. The fabrication strategies, advantages, multifunctionalities, and energy storage applications, along with their inherent structure–activity relationships, are comprehensively discussed. The challenges and future perspectives associated with the MXene binder are also highlighted, aiming to offer a foundational reference for developing advanced binder systems for next‐generation, high‐performance ESSs.
Atomically Dispersed Iron‐Catalyzed Aerobic Hydroxylation of Allylic and Propargylic C─H Bonds
ABSTRACT Selective functionalization of carbon–hydrogen bonds represents a central goal in modern organic synthesis, yet achieving site‐ and chemoselective oxidation using molecular oxygen remains a longstanding challenge. In particular, aerobic hydroxylation of allylic and propargylic C─H bonds is difficult due to overoxidation and competing side reactions. Here we report a heterogeneous catalyst featuring atomically dispersed iron sites embedded in a nitrogen‐doped carbon matrix. This catalyst enables unprecedented site‐ and chemoselective allylic and propargylic C─H hydroxylation of alkenes and alkynes using air as the oxidant at 30°C. The method accommodates a broad range of terminal and internal substrates with excellent functional‐group tolerance and enables late‐stage oxidation of structurally complex molecules. Mechanistic studies demonstrate that the catalytic activity originates from highly dispersed FeN x sites. This work highlights the potential of single‐atom catalysis to address fundamental challenges in sustainable C─H oxidation and expands the toolbox for selective oxidative transformations.
Polymeric Sorbents as Energy‐Efficient Alternative to Cryogenic Distillation for Light Hydrocarbon Purification
ABSTRACT Light hydrocarbons are essential gaseous compounds for fuel, polymer manufacturing, fertilizer production, and so forth. The efficient recovery and purification of these gases are still challenging despite their significant industrial and domestic relevance. They exist in the gaseous state under ambient temperature and pressure and are typically recovered from natural gas streams containing multiple close‐boiling‐point hydrocarbons. So far, cryogenic distillation is the commonly used method for their separation and purification. It operates based on their boiling‐point differences, which amounts to significant energy consumption. To address this limitation, adsorption‐based technology is considered an energy‐efficient alternative for the purification of light hydrocarbons. To this effect, polymeric sorbents such as porous polymer networks (PPNs) are a potential alternative due to their robustness, stability, and scalability. This review provides an extensive discussion on cryogenic distillation, applications of light hydrocarbons, and progress in light hydrocarbon purification using polymeric sorbents. Additionally, the pore structure, stability, and techno–economic feasibility of the polymeric sorbents were extensively examined, covering current progress, mechanism of guest molecule separation, characterization techniques, and hurdles still encountered. Overall, since their application in light hydrocarbon separation is still an evolving field, this review will facilitate robust designs by providing the necessary know‐how and roadmaps needed for advancement.
Geoscience‐Inspired Pore Topology Engineering for Ultra‐Thick Cathodes Toward High‐Energy‐Density Zinc‐Ion Batteries
ABSTRACT Zinc‐ion batteries (ZIBs) are promising for safe and large‐scale energy storage, yet the construction of high‐performance ultrathick and high‐loading cathodes hinders their application due to sluggish ion/electron transport. Herein, drawing upon the structure‐activity relationships of pore topology in geoscience, we propose an efficient pore network regulation strategy using an ammonium acetate porogen to prepare a high‐performance ultrathick cathode through integrating this architecture with a graphene/carbon nanotubes framework synergistically enhances both ionic and electronic conductivity. Specifically, micro‐computed tomography (Micro‐CT) and pore network modeling reveal a highly optimized pore topology with remarkably increased connectivity (64.9%), coordination number (77.8%), and throat diameter (25%) despite a mere 13% increase in porosity by using ammonium acetate porogen. This architecture preserves conductive network robustness during wetting and enhances mass/ion transport, as validated by Avizo permeability simulations. As expected, the cathode delivers 17.96 mAh cm −2 (97.2% retention after 106 cycles) and a competitive energy density of 152.8 Wh kg −1 (N/ P = 1.3) in coin cells with an ultra‐high loading of 56.8 mg cm −2 . A practical 4 × 4.5 cm pouch cell using this cathode achieves a full‐cell energy density of 69.2 Wh kg −1 as well as82.6% retention over 96 cycles. This scalable topology‐guided strategy bridges geoscience and battery engineering for ZIBs.
Homogeneous/Heterogeneous Catalyst Design for Lithium–Sulfur Batteries via Phase Separation
ABSTRACT The dual regulation of sulfur redox kinetics and lithium deposition behavior represents a pivotal breakthrough toward overcoming the performance limitations of lithium–sulfur (Li–S) batteries. Metal‐based organic molecules provide an ideal solution for rationalizing the electrolyte electrochemistry in Li–S system, featuring both nitrogen‐rich properties and active metal centers. Herein, we leverage the solubility of iron phthalocyanine chloride (FePcCl) in the electrolyte to induce phase separation. The dissolved portion (FePcCl solute) functions as a homogeneous catalyst (Fe‐Hom), whilst the insoluble fraction is uniformly loaded onto carbon spheres to act as a heterogeneous catalyst (Fe‐Het). The homogeneous/heterogeneous synergistic catalyst system (Fe‐Syg), developed through precise phase‐separation engineering, enables the coexistence of mobile and immobilized active sites. This synergy maximizes the working activity of Fe‐Syg beyond the limitations of single‐phase catalysts, simultaneously regulating sulfur conversion kinetics and lithium plating/stripping behavior toward high‐efficiency and robust electrodes. As a result, the Li–S batteries incorporating Fe‐Syg demonstrate favorable rate capability and operational lifespan under various conditions. Remarkably, a pouch cell assembled with a lean electrolyte dosage of 3.5 µL mg −1 achieves a favorable energy density of 364.8 Wh kg −1 and maintains stable cycling for 40 cycles.
Spatial Control of Light‐Responsive Proteins and Optogenetics Within Hydrogels via Volumetric Bioprinting
ABSTRACT Spatiotemporal control over cell fate and behavior within bioprinted constructs remains a key challenge in tissue engineering. Optogenetics offers versatile potential for non‐invasive regulation of biological processes. Yet, its integration within large‐scale, cell‐laden bioprinted materials is still limited, especially considering the spatial constraints of existing light delivery methods. In this study, we introduce a novel approach that repurposes tomographic volumetric bioprinting to enable post‐printing stimulation of photosensitive protein‐switches and optogenetic circuits in cells deep within hydrogel constructs. By converging different bioprinting approaches, computer vision, context‐aware model generation, and synthetic biology and cell engineering, we demonstrated selective activation of a fluorescent, light‐responsive protein probe within multi‐material centimeter‐scale constructs. Moreover, leveraging a multi‐wavelength volumetric bioprinter, we further demonstrate this concept by selectively stimulating cells expressing a near‐infrared optogenetic system that triggers gene expression and the induction of pancreas‐specific transcription factors. The described methods provide platforms for remote, repeatable, and localized control of biological events in volumetric constructs, opening new possibilities for advanced tissue models, and dynamic tuning of cell‐mediated protein production in engineered living systems.