Browse Articles

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.

Atroposelective Dearomative Cross‐Coupling of Benzofuran Derivatives by Z‐Selective Functionalization of the Vinyl C─O Bond

ABSTRACT Catalytic asymmetric transformation of benzofuran derivatives has received significant attention owing to its capacity to prepare chiral molecules from readily available feedstocks. Herein, an unprecedented asymmetric cross‐coupling of benzofuran derivatives is reported for the construction of axial chirality. Employing a chiral nickel catalyst, this approach is achieved through direct enantio‐ and Z‐selective dearomative functionalization of the vinyl C─O bond, providing efficient access to valuable atropisomeric acyclic alkenes. A broad substrate scope is demonstrated under mild conditions. Moreover, experimental and theoretical mechanistic studies suggest that the stereochemical outcome is facilitated by a dynamic epimerization between diastereomeric six‐membered ( Z )‐styryl‐nickelacycle intermediates.

Simultaneous Enhancement of Charge Transport and Stretchability for IDTBT Polymer Semiconductor via Partial Substitution of Long Alkyl Chains With Cyclopentyl Groups

ABSTRACT Polymer semiconductors that simultaneously exhibit high charge mobility and robust mechanical stretchability are essential for the next generation of flexible electronics. Here, we report a new poly(indacenodithiophene‐ alt ‐benzothiadiazole) ( IDTBT ) based polymer semiconductor, IDTBT‐C‐1 , in which a fraction of the long alkyl chains are replaced with cyclopentyl groups, exhibiting a hole mobility of 6.01 cm 2 V −1 s −1 , among the highest reported for intrinsically stretchable polymer semiconductors to date, and substantially higher than that of the parent IDTBT (1.39 cm 2 V −1 s −1 ). Notably, the charge transport performance of IDTBT‐C‐1 remains highly stable even after 3000 stretching‐releasing cycles at 50% strain. Moreover, relative to the parent IDTBT , IDTBT‐C‐1 exhibits a higher onset strain for surface damage, an increased elastic modulus, and enhanced strain recovery. Further studies reveal that substitution with a cyclopentyl group strengthens interchain interactions among conjugated units. These reinforced interactions facilitate interchain charge hopping, leading to enhanced mobility, while simultaneously promoting the formation of additional physical cross‐links that impart superior mechanical stretchability and elastic recovery to IDTBT‐C‐1 thin films.

Outside Back Cover: Selective Synthesis of [2]Rotaxane Orientational Isomers With Precisely Arranged Luminogens: Toward Orientation‐Dependent Emissions for Information Storage and Encryption (Angew. Chem. Int. Ed. 33/2026)

Coordination‐Engineered Interfacial Pathway Partitioning for Electrocatalytic CO ₂ Conversion and Downstream Upgrading

ABSTRACT Electrochemical CO 2 reduction (eCO 2 RR) is increasingly capable of delivering downstream‐compatible carbon products, yet the interfacial origin of pathway selection remains insufficiently understood. Here, coordination‐environment‐tunable Cu–Sn catalysts are employed to partition CO 2 electrosynthesis between a Sn‐centered formate‐selective pathway and a Cu‐centered CO‐selective pathway. In situ spectroscopy reveals coordination‐dependent evolution of adsorbed intermediate and interfacial water structures, while H/D kinetic isotope analysis and in situ electrochemical impedance spectroscopy‐distribution of relaxation times (EIS‐DRT) measurements resolve distinct proton‐coupled and polarization‐sensitive kinetic regimes. Density functional theory calculations further elucidate the energetic origin of pathway bifurcation through coordination‐dependent reconstruction of adsorption geometry and interfacial energetics. Sn‐centered medium‐coordination regimes favor oxygen‐bound intermediates and a proton‐coupled formate pathway, whereas Cu‐centered medium‐coordination regimes promote carbon‐bound adsorption and CO‐selective reactivity. In the downstream modules, electrodialysis achieves a 98.1% HCOOK‐to‐HCOOH conversion with 93.97% Faradaic efficiency (FE) at 300 mA cm −2 , while CO 2 ‐NH 3 route delivers formamide with a maximum FE of 45.2% and a production rate of 840 µmol cm −2 h −1 . This work establishes coordination‐engineered interfacial partitioning as a strategy for integrated CO 2 electrosynthesis with downstream upgrading.

Ultrasound‐Driven Interfacial Electron Modulation Reprograms Mitochondrial Metabolism for Glioblastoma Therapy

ABSTRACT Glioblastoma (GBM) remains difficult to treat because the restrictive blood–brain barrier (BBB), the hypoxic tumor microenvironments, and mitochondrial electron transport chain (ETC)‐driven metabolic adaptability jointly limit therapeutic delivery and efficacy. Selective disruption of mitochondrial metabolism in GBM is challenging because ETC function is also essential for normal brain cells, and many therapeutic agents show limited BBB penetration or reduced activity under oxygen‐limited conditions. Here, we report Ni/LDH@M, an ultrasound‐responsive biomimetic Schottky nanoplatform assembled from nickel nanosheets and layered double hydroxide (LDH) nanosheets and cloaked with GL261 glioma cell membranes to enable homotypic recognition and accumulation in orthotopic glioma. Upon ultrasound irradiation, Ni/LDH@M drives carbon monoxide (CO) generation through interfacial electron modulation, and the generated CO inhibits mitochondrial cytochrome c oxidase, disrupts ETC electron transfer, and induces mitochondria‐dependent apoptosis and immunogenic cell death (ICD). In mice bearing orthotopic GL261 gliomas, ultrasound‐activated Ni/LDH@M suppressed tumor progression and prolonged survival, showing that controlled CO generation can reprogram tumor‐cell mitochondrial metabolism for GBM therapy.

Coordination Engineering of Ir─Mo Atomic Pair Sites to Break Scaling Limitations for Acidic Oxygen Evolution

ABSTRACT Coordination engineering of single‐atom catalysts (SACs) is a powerful strategy to address durability and activity challenges in the acidic oxygen evolution reaction (OER). Here, we obtain two distinct Ir single‐atom configurations on MoO 3 support by regulating the second‐shell coordination environment. Compared with the weakly interacting Ir─O─Mo structure, atomic pair sites formed through direct Ir─Mo coordination exhibit strong electronic coupling with the support, thereby enhancing atomic dispersion and structural stability. In situ experimental and theoretical studies reveal that the Ir─Mo pair sites trigger a new oxide‐mediated pathway, in which dynamic hydroxyl spillover from Mo to Ir site effectively facilitates *OOH formation. This process breaks the linear scaling relationship between *OH and *OOH adsorption, lowering the energy barrier of the rate‐limiting step and enabling superior OER kinetics. As a result, the Ir O+Mo /MoO 3 catalyst achieves outstanding stability for over 1500 h at 10 mA cm −2 in acidic electrolyte and sustains continuous operation for 300 h at 1.0 A cm −2 in the proton exchange membrane water electrolyzer. This work provides novel insights into the coordination engineering of SACs and opens a promising avenue for overcoming scaling limitations in acidic OER catalysis.

Electrolyte Design for Fast‐Charging Lithium‐Based Batteries

ABSTRACT Fast charging is essential for the widespread adoption of lithium (Li)‐ion batteries, but it is fundamentally limited by sluggish interfacial kinetics, Li plating, and electrolyte instability at high current densities. Over the past decade, electrolyte engineering has emerged as a key strategy to address these challenges. This review summarizes the development of fast‐charging electrolytes over the past ten years and outlines a design framework. Electrolyte formulations are first deconstructed into their main components—solvents, salts, and functional additives—and representative strategies for tuning solvation structure and interphase chemistry are discussed to suppress Li plating and improve interfacial kinetics. The discussion then extends to advanced electrolyte systems, particularly localized high‐concentration electrolytes (LHCEs), and their compatibility with different anode chemistries. Advanced characterization techniques are also summarized and categorized based on destructiveness, spatial and temporal resolution, quantitative analysis, and the chemical species or processes probed across multiple length scales. Recent progress in AI‐enabled electrolyte discovery and battery management system (BMS) strategies for optimized fast‐charging protocols is further highlighted. Finally, perspectives are presented on translating electrolyte innovations from academic research to practical applications, with emphasis on cell format, realistic operating conditions, and manufacturability.

Bridging the Gap to Practical Aqueous Zinc–Iodine Batteries: Advanced Hydrogel Electrolytes via Interfacial Chemistry and Architectural Engineering

ABSTRACT Aqueous zinc–iodine (Zn–I 2 ) batteries are promising for grid‐scale storage and flexible electronics because of their nonflammable chemistry, low cost, and high theoretical capacity. Their deployment, however, is limited by uneven Zn deposition, water‐driven hydrogen evolution and corrosion, and polyiodide shuttling. Functional hydrogel electrolytes can regulate these coupled processes through solvent confinement, ion‐selective transport, and mechanically persistent electrode contact. This review critically examines recent advances in hydrogel electrolytes for Zn–I 2 batteries from interfacial chemistry to architectural engineering. Distinct from broader hydrogel reviews for aqueous Zn batteries, it focuses on the chemically asymmetric coupling between a water‐reactive Zn anode and a soluble polyiodide cathode and organizes the field through a structure–mechanism–performance framework that links molecular affinity, fixed charge, and water‐state regulation to measurable interfacial parameters, spatially decoupled architectures, and scale‐relevant device metrics. We analyze dual‐interface regulation across solvation and nucleation, polyiodide confinement, tortuosity control, and asymmetric/Janus structures. Broad‐temperature and voltage‐tolerant operation, together with self‐healing, self‐sensing, and biosensing functions, is also evaluated. Finally, we distinguish materials‐level evidence from pouch‐ and Ah‐level validation and propose an application‐specific roadmap centered on high iodine loading, lean electrolyte, limited Zn inventory, water retention, and scalable manufacturing.

Nonvolatile Electrical Control of Spin‐Polarized Tunneling via Sublattice‐Asymmetric Interfacial Magnetoelectric Coupling

ABSTRACT Achieving nonvolatile, all‐electric control of spin‐dependent transport properties remains a fundamental challenge in spintronics. Here, we demonstrate nonvolatile electric‐field‐driven control of spin‐polarized tunneling in a multiferroic tunnel junction based on a compensated CoGd ferrimagnet. By switching the ferroelectric polarization, we achieve a clear sign inversion of the tunneling magnetoresistance (TMR), clearly indicating the all‐electric control of the spin‐polarized tunneling. Crucially, the opposite polarity of the TMR sign switching observed above and below the magnetic compensation temperature unambiguously proves that this behavior is intrinsically tied to ferrimagnetism. This phenomenon is governed by a synergistic mechanism: the electric field disparately modulates the antiferromagnetically coupled sublattices while simultaneously driving an interfacial electronic reconstruction that inverts the spin polarization at the Fermi level. Exploiting this intrinsic sublattice asymmetry in ferrimagnets elegantly circumvents traditional magnetic switching paradigms, establishing a framework for next‐generation spintronic architectures.

Dual‐Binder‐Enabled 18‐µm‐Thick High‐Conductivity Sulfide Electrolyte Film for High‐Energy‐Density All‐Solid‐State Batteries

ABSTRACT The development of ultrathin, high ionic conductivity sulfide solid‐state electrolytes (SSEs) film is essential for achieving high‐energy‐density all‐solid‐state batteries (ASSBs). However, conventional chemically inert binders inevitably impede Li‐ion transport kinetics within SSE films, and the underlying Li‐ion transport mechanisms remain elusive. In this work, we report an Li‐ion‐conductive polymer binder (LiTFSI‐PMEMA) and integrate it with SSEs via dry processing to fabricate an ultrathin SSE film (USF). The resulting USF is only 18 µm thick and exhibits a high ionic conductivity of 1.56 mS cm ‒1 . By combining cryogenic transmission electron microscopy (cryo‐TEM), solid‐state nuclear magnetic resonance (ssNMR), and theoretical simulations, we propose an Li + transport model in which the SSE phase provides the dominant conduction pathway, while the polymer binder and SSEs/polymer contact regions can assist local Li + transport continuity between neighboring SSE particles. When implemented in ASSBs, the USF exhibits exceptional interfacial compatibility and kinetic stability, enabling a long‐term cycling life with 70.3% capacity retention over 1500 cycles. Furthermore, a LiNi 0.7 Co 0.2 Mn 0.1 O 2 ||USF||nSi pouch cell delivers a high stack‐level energy density of 322.7 Wh kg ‒1 . This work provides crucial insights into the multiphase Li‐ion transport kinetics and demonstrates a scalable manufacturing strategy for sulfide‐based ASSBs.

Closed‐Loop Solid‐State Synthesis Planning for Materials Discovery With Large Language Models

ABSTRACT Developing reliable synthesis routes for complex materials remains a major bottleneck in accelerating materials discovery. This study establishes a large language model‐based framework for predicting and optimizing synthesis conditions directly from the literature data. Key synthesis information, including target compounds, precursors, and processing parameters, was systematically extracted from 4407 open‐access solid‐state synthesis papers and organized into a structured recipe dataset. Using a retrieval‐augmented generation (RAG) approach, the system first retrieves similar recipes from the corpus and then generates a new candidate recipe conditioned on those exemplars. The generated recipes were benchmarked against literature data using quantitative scoring metrics, achieving strong agreement with experimentally reported conditions. To validate the predictive capability, the framework was applied to unreported solid‐state electrolyte candidates identified through first‐principles screening, and multiple oxy‐selenide compounds were successfully synthesized through iterative feedback between the model and experiment. The recipe generator accurately refined synthesis parameters over successive trials, demonstrating its ability to reproduce phase‐pure products while minimizing trial‐and‐error. This approach establishes a data‐driven, feedback‐optimized route to accelerate synthesis design, offering a generalizable paradigm for integrating language models into experimental materials research.

Intracellular Proton Enrichment Drives Unified Dual‐Cofactor Regeneration for Biohybrid CO ₂ Fixation

ABSTRACT Photocatalytic biohybrid systems, which interface photosensitizers with whole‐cell biocatalysts, represent a platform for sustainable solar‐to‐chemical CO 2 conversion. However, their efficiency is fundamentally constrained by kinetic mismatch between sluggish transmembrane electron injection and uncoupled proton flux required for bioenergetic transduction. This uncoupling restricts the regeneration of adenosine triphosphate (ATP) and reduced nicotinamide adenine dinucleotide (NADH), the dual cofactors essential for driving carbon fixation pathways. Here, we introduce a proton enrichment strategy utilizing protonated manganese‐doped carbon dots (HMnCDs) that function simultaneously as reversible proton buffers and photoelectron donors. HMnCDs localize to the periplasm of Cupriavidus necato r H16, where their labile protons reinforce the transmembrane proton gradient driving ATP synthase. Concurrently, cytoplasmic HMnCDs facilitate proton‐coupled electron transfer, accelerating NADH photoregeneration. The concerted management of proton and electron fluxes decouples ATP generation from respiratory NADH oxidation, creating a synergistic cofactor supply even under electron transport chain inhibition. Consequently, the biohybrid achieves light‐driven autotrophic growth and poly(3‐hydroxybutyrate) biosynthesis from CO 2 , attaining a record quantum efficiency of 20.8%. Multi‐omics analyses reveal global metabolic reprogramming, including upregulated carbon fixation pathways and adaptive modulation of energy homeostasis under the proton‐enriched microenvironment. This work establishes proton enrichment as a generalizable design principle for coupling photochemistry with cellular bioenergetics.

Trace Aqueous Humor Proteome via Macroporous MOF Platform Reveals High‐Resolution Molecular Phenotypes of Diabetic Macular Edema

ABSTRACT Diabetic macular edema (DME) is a leading cause of vision impairment worldwide. While aqueous humor (AH) proteomics holds promise for uncovering disease mechanisms and biomarkers, its proteome coverage has been constrained by limited sample volume and low protein concentration. Here, we present quaternary lanthanide‐based macroporous metal–organic frameworks to enrich AH proteins and a corresponding streamline for ultrasensitive trace aqueous humor proteome (TAHP). TAHP permits end‐to‐end sample‐to‐result analysis in <4 h and quantifies >3300 proteins from merely just 1 µL AH. Applied to cataract ( n = 31) and DME ( n = 52) clinical cohorts, TAHP delineated DME molecular landscape and uncovered proteomic signatures of pathological angiogenesis, amplified inflammatory signaling, and compromised antioxidant defenses. By integrating machine learning, we prioritized PAFAH2 as a high‐performance single biomarker for DME stratification (AUC = 0.98 ± 0.02). TAHP enables rapid, robust and deep AH proteomics, offering a broadly accessible platform to decipher proteome atlas across fundus diseases not limited to DME.

Self‐Growing Conductive Hydrogels Establish Volumetric Biointerfaces for Cardiac Conduction Restoration

ABSTRACT Restoring three‐dimensional electrical conduction in infarcted myocardium remains a critical challenge, as conventional conductive hydrogel patches largely remain surface‐confined and prevent electrical coupling of residual cardiomyocytes within fibrotic scars. Here, we present a self‐growing conductive volumetric interface (SCOVE) that transforms surface‐confined biointerfaces into tissue‐integrated, three‐dimensional conductive networks. SCOVE is delivered as an injectable hydrogel precursor containing the tissue‐permeable conductive monomer 3,4‐ethylenedioxythiophene‐acetic acid sodium salt (ETE), which rapidly infiltrates infarcted myocardium and undergoes endogenous glucose‐triggered oxidative polymerization to self‐grow a conductive polyETE network in situ. The resulting hydrogel gels within 1 min, reaches cardiac‐mimetic conductivity (∼1 S m − 1 ) within 45 min, and preserves native myocardial mechanics without inducing tissue stiffening. In a rat myocardial infarction model, SCOVE penetrates the infarct, reduces scar resistivity by 2.54‐fold compared with conventional 2D conductive patches, restores electrical coupling among residual cardiomyocytes, enhances Cx43 expression, and accelerates impulse propagation. By replacing static, surface‐confined conductive patches with self‐growing volumetric biointerfaces, this work establishes a generalizable strategy for reconstructing tissue electrophysiology and advancing bioelectronic therapies for myocardial infarction and other electrically dysfunctional tissues.

Waterborne Interfacial‐Reinforcement Strategy for Sustainable Natural Rubber Latex Bioelastomers With Self‐Healing, Crack Tolerance, and Multifunctional Durability

ABSTRACT Developing bio‐based elastomers that combine mechanical robustness, crack tolerance, self‐healing, and functional durability remains challenging. Here, we report a waterborne interfacial reinforcement and functionalization strategy to construct multifunctional natural rubber latex (NRL)‐based bioelastomers. Ammonium persulfate (APS)‐assisted treatment promotes interfacial coupling between NRL chains and cellulose nanofibers (CNFs), establishing nanofiber‐mediated load‐transfer and energy‐dissipation pathways. ZnO nanoparticles introduce inorganic physical junctions that regulate interfacial stress transfer while providing UV shielding and antibacterial activity. The optimized NRL‐g‐CNF/ZnO composite exhibits a tensile strength of 9.68 MPa, toughness of 15.30 MJ·m −3 , and efficient room‐temperature self‐healing, with tensile strength and toughness recovery of 96.9% and 92.8% after 48 h, respectively. The composite also shows pronounced crack tolerance, including a fracture energy of 32.5 kJ·m −2 and stable deformation of notched samples, together with improved short‐term mechanical retention under the specified UV‐aging conditions, antibacterial activity, a measurable soil‐burial response, and preliminary cytocompatibility. This simple casting‐based strategy provides a potentially scalable route to multifunctional bioelastomers with potential for selected packaging applications, protective coatings, antibacterial/UV‐shielding films, and non‐implantable flexible materials.