Browse Articles

Defect‐Engineered Microwave‐Responsive Ni@C Composites From Waste PET for Catalytic Plastic Upcycling

ABSTRACT Direct catalytic upcycling of solid plastic waste is challenging owing to its chemical robustness, and existing conversion routes often require harsh conditions or costly catalysts. Here, we develop a circular plastic‐to‐catalyst‐to‐product strategy converting waste poly(ethylene terephthalate) (PET) bottles into a microwave‐responsive composite catalyst for microwave‐assisted catalytic plastic upcycling. First, microwave‐assisted PET depolymerization and Ni‐MOF nanorod crystallization generate abundant missing‐cluster defects, inherited during pyrolysis as lattice‐distorted Ni nano‐cores and edge dislocations encapsulated within a defective carbon shell (Ni@C). These strain‐rich Ni─C heterointerfaces enhance dielectric loss and interfacial polarization under microwave irradiation, promoting local microwave energy dissipation at catalyst‐plastic contacts and accelerating peroxymonosulfate (PMS) activation. Coupled microwave‐thermal‐chemical PMS activation initiates polymer‐chain disordering, hydrogen abstraction, and C─C bond scission in high‐density polyethylene (HDPE) particles before oxidative functionalization, making it more efficient than oxidation‐dominated hydrothermal heating. Spectroscopic and strain‐mapping analyses reveal that dislocation‐rich Ni cores and carbon defects govern microwave energy dissipation and thus catalytic oxidation reactivity. The optimized Ni@C catalyst achieves up to 96% degradation of HDPE and converts products into valuable liquid hydrocarbons and oxygenates with limited phytotoxicity. Overall, this work integrates waste‐derived catalyst design with microwave‐assisted plastic conversion, offering a route toward circular plastic upcycling and carbon recovery.

A Two‐Dimensional Organic–Inorganic Hybrid Perovskite Ferroelectric for High‐Performance Composite Magnetoelectric and Dual‐Source Energy Harvesting

ABSTRACT Magneto‐mechano‐electric (MME) generators capable of simultaneously harvesting ubiquitous vibrational and magnetic‐field energy are attractive candidates for self‐powered systems. However, existing inorganic ceramic and polymeric materials are fundamentally constrained by a trade‐off among transverse piezoelectric performance, manufacturability, and mechanical compliance, thereby limiting further advances in MME coupling. Here, we report a new Ruddlesden–Popper (RP)‐type molecular ferroelectric, [DFCBA] 2 CdCl 4 ( 1 ; DFCBA = 3,3‐difluorocyclobutylammonium), which exhibits a large transverse piezoelectric response. Owing to the pronounced structural anisotropy of its layered framework, preferentially oriented 1 @PVA composite films can be readily fabricated on Metglas substrates by simple spin coating. A cantilever‐type MME generator based on this composite delivers a magnetoelectric (ME) voltage coefficient of 450 V cm −1 Oe −1 at approximately 50 Hz after geometric optimization, representing one of the highest ME voltage coefficients reported to date for molecule‐based ME composites. The device also enables the simultaneous harvesting of magnetic‐field and vibrational energy, exhibiting a pronounced energy‐superposition effect under dual excitation and stable electrical output under practical operating conditions. These findings establish RP‐type molecular ferroelectrics as a promising materials platform for high‐performance MME generators and open new opportunities for multi‐source energy harvesting and self‐powered Internet of Things technologies.

Hydroxylation Regulated Polar Interfaces for Enhanced Contact‐Electro‐Catalysis

ABSTRACT Contact‐electro‐catalysis (CEC) converts mechanical excitation into interfacial redox chemistry, yet polar mineral water interfaces remain insufficiently engineered, limiting the efficient translation of spontaneous polarization into contact driven charge transfer. Here, we use surface hydroxylation to regulate the polar interface of natural tourmaline for enhanced CEC. Experiments and first principles calculations show that hydroxyl groups preferentially anchor at surface Al sites, forming a hydroxyl enriched interface while preserving the bulk crystal framework. This interface reorganizes the charge distribution, enhances effective interfacial polarization, raises the surface potential, and reduces charge transfer resistance, thereby facilitating H 2 O and O 2 activation. Under ultrasound excitation, hydroxylated tourmaline produces ·OH and ·O 2 − signals 6.5 and 5.7 times higher, respectively, than those generated by spontaneous polarization alone. The enhanced CEC enables Rhodamine B degradation, heavy metal removal, and antibacterial activity. This work establishes hydroxylation regulated polar interfaces for mechanically driven environmental catalysis.

Chlorination‐Induced Symmetry Breaking in Cu Single‐Atom Sites for Boosting Electrocatalytic Nitrate Reduction to Ammonia

ABSTRACT Electrochemical nitrate reduction to ammonia is attractive for green fertilizer synthesis and pollution remediation, yet its performance is normally hindered by the mismatched generation and consumption of active hydrogen (*H). Here, we engineer the planar chloride coordination to break the local symmetry of Cu single atoms over oxygen‐deficient WO 3‐x , forming Cu 1 Cl–WO 3‐ x with Cu–O/Cl and Cu–Cl–W motifs to enable dual interfacial relay of *H and *NO 2 derived intermediates. The Cu 1 Cl–WO 3‐ x catalyst achieves an NH 3 Faradaic efficiency of 99.7% at −0.8 V versus the reversible hydrogen electrode and delivers an NH 3 yield rate up to 63.6 mg h −1 cm −2 at −0.9 V with stable operation. In situ electrochemical characterization and theoretical calculations reveal that the asymmetric Cu–Cl–W interface promotes water dissociation and *H relay, while facilitating thermodynamically favorable *NO 2 relocation and subsequent hydrogenation, thereby shifting the potential‐determining step and lowering the overall energy barrier. This dual‐relay strategy might offer a generic route toward efficient NO 3 − ‐to‐NH 3 electrosynthesis.

Predesigned Carbon Vacancies Unlock Superior Oxidation Resistance of High‐Entropy Carbides by Stabilizing a Protective M–C–O Interphase

ABSTRACT The initial oxidation stage of high‐entropy carbides (HECs) is a decisive yet poorly understood “black box” that governs their ultimate performance for ultra‐high‐temperature applications. Here, we unveil a powerful strategy—predesigning carbon vacancies—to fundamentally enhance HECs oxidation resistance. By integrating in situ x‐ray diffraction (XRD) and in situ transmission electron microscopy coupled with electron energy loss spectroscopy (TEM‐EELS), we provide the first direct, atomic‐scale visualization of oxygen atoms preferentially occupying these predesigned vacancies during the incipient oxidation stage, leading to the dynamic formation of a metastable metal–carbon–oxygen (M–C–O) interfacial layer. Our combined experimental and theoretical analyses reveal a dual enhancement mechanism: kinetically, M–C–O suppresses both oxygen adsorption on the (111) surface and its subsequent inward diffusion; thermodynamically, they stabilize the HEC lattice at elevated temperatures, thereby increasing the energy barrier for M─C bond cleavage. This work not only deciphers the atomistic origin of enhanced oxidation resistance but also establishes a simple, general, and efficient design principle for next‐generation ultra‐high‐temperature ceramics.

Pressure‐Treated Luminescent and Structural Evolution With Irreversible Control of Emission in Through‐Space Charge Transfer Emitter

ABSTRACT Through‐space charge transfer (TSCT) is gaining prominence for developing solid‐state luminophores, owing to its tunable and dynamically regulable luminescence. In this work, a novel TSCT emitter with a spatially segregated donor–acceptor (D–A) architecture is designed and synthesized, which exhibits high‐efficiency blue‐violet emission at 410 nm with a narrow 37 nm FWHM and minimal Stokes shift due to molecular rigidity and suppressed structural reorganization. DMAC‐CBO crystal demonstrates remarkable mechanochromism through grinding‐induced amorphization and a pronounced piezochromic response showing a 156 nm redshift in the range of 14.0 GPa due to the decreased distance between D and A units. As a result, pressure‐induced the enhancement of intramolecular and intermolecular interactions promote excimer formation, leading to redshifted emission and enabling the modulation of the dominant emissive state from a local excited (LE) state to an excimer. Impressively, upon decompression from high pressure, DMAC‐CBO retains a metastable phase, resulting in irreversibly shifted and broadened luminescence derived from excimers. These findings not only demonstrate that pressure can continuously regulate the distance between D and A units of TSCT‐based materials, but also effectively establish a structure‐property framework for TSCT‐based smart materials with tunable and persistent emission, offering promising applications in data storage, sensing, and optoelectronics.

Active Phase of Nickel Electrocatalysts Driving Alkaline Hydrogen Evolution

ABSTRACT Nickel‐based cathodes are widely used in alkaline water electrolysis, yet the nature and stability of the active surface under operating conditions remains unclear. In particular, the role of metal/oxo–hydroxo interfacial structures in governing hydrogen evolution activity is not well understood. Here, we employ a multimodal, depth‐sensitive approach combining operando Ni L‐edge X‐ray absorption spectroscopy, depth‐sensitive X‐ray absorption measurements in total electron yield and Auger electron yield modes, X‐ray photoelectron spectroscopy, isotopically labeled nano secondary ion mass spectrometry, and online electrochemical mass spectrometry to directly track the evolution of Ni/NiO x H y interfaces during the hydrogen evolution reaction. Using well‐defined sputtered Ni thin films as a model system, we show that progressive reduction of near‐surface oxide/hydroxide species is accompanied by a gradual loss of hydrogen evolution activity. Depth‐resolved measurements reveal a predominantly metallic outermost surface under cathodic bias, while NiO x H y forms on the surface upon relaxation to open‐circuit conditions. Importantly, mild anodic pre‐conditioning regenerates subsurface NiO x H y species, resulting in a sustained increase in hydrogen evolution activity upon subsequent cathodic polarization. These results establish the crucial role of metal/oxo–hydroxo interfaces as active phases for hydrogen evolution and provide a framework for engineering robust, Earth‐abundant HER cathodes capable of operating under dynamic, real‐world electrolysis conditions.

Hydrophilic RuGd Alloy Redirecting Interfacial Water Adsorption Configuration for Long‐Term and Ampere‐Level Hydrogen Evolution

ABSTRACT Rapid interfacial water dissociation is pivotal to efficient hydrogen evolution reaction (HER) in anion‐exchange‐membrane water electrolysis (AEMWE), whereas its effective modulation remains a great challenge. Herein, we develop a hydrophilic RuGd alloy supported on carboxylated lignin‐derived carbon (RuGd/CLC) enabling rapid interfacial water dissociation for long‐term and ampere‐level hydrogen production. The RuGd/CLC as a cathode catalyst of AEMWE cell can achieve 1.0 A cm −2 at only 1.685 V and sustains continuous operation for over 1200 h with a degradation rate of only 10 µV h −1 . It is discovered that the hydrophilic Gd induces local charge redistribution and interfacial oxyphilic site that strengthens O‐end interaction of H 2 O at the alloy interface, which redirects adsorbed H 2 O from a parallel configuration on Ru to a more polarized asymmetric H‐down configuration. This reorientation is accompanied by unequal O─H bond elongation and hydrogen‐bond‐network reconstruction from a bound state toward free water, which reduces water dissociation energy barriers to continuously supply sufficient protons in HER. This work provides an effective rare earth induced redirection strategy for accelerating interfacial water dissociation and high‐performance hydrogen production.

Tailoring Unconventional Cyanogen Defect in High‐Entropy Prussian Blue Cathode Material for Advanced Sodium‐Ion Batteries

ABSTRACT High‐entropy Prussian blue analogues (PBAs) are promising cathodes for sodium‐ion batteries (SIBs). However, inherent [Fe(CN) 6 ] 4– defects deteriorate electrochemical kinetics and phase stability. Herein, an unusual cyanide (CN – ) vacancy is tailored in high‐entropy PBA (HE‐Cu‐PA, Na 1.58 Mn 0.191 Fe 0.2 Co 0.195 Ni 0.2 Cu 0.19 [Fe(CN) 5.85 ]), constructed via a phytic acid (PA) assisted coprecipitation method, as cathode material for SIBs. The precisely designed high‐entropy composition with CN – defects create adaptive coordination flexible sites and local electronic delocalization regions, synergistically enhancing structural stability, electrochemical dynamics, and redox reversibility. The large‐sized [Fe(CN) 6 ] 4– vacancy in PA‐free high‐entropy PBA (HE‐Cu) exhibits poor electronic transfer capability and accumulated lattice strain, while static local lattice distortion generated by Ti 3+ N 6 octahedron in high‐entropy composition (HE‐Ti‐PA) causes large lattice stress and Na‐ion diffusion barrier. The complex structural evolution (monoclinic ↔ cubic ↔ tetragonal) originated from Jahn–Teller effect and octahedron instability can be completely restrained in HE‐Cu‐PA, achieving a zero‐strain solid‐solution Na‐ion storage mechanism, where Mn, Fe, Co, and Cu‐ions act as redox sites for charge compensation. Therefore, HE‐Cu‐PA delivers high initial capacity of 117.6 mAh·g −1 , superior rate capability and ultra‐long lifespan over 6000 cycles with ultra‐low decay‐rate of 0.0085% per cycle. And ultra‐long cycling lifetime over 4000 cycles can be acquired for high‐energy‐density (338.0 Wh·kg −1 ) quasi‐solid‐state Na‐ion full batteries.

Chirality‐Induced Selective Electrosynthesis Hydrogen Peroxide and Tandem Green Chemical Synthesis

ABSTRACT Two‐electron oxygen reduction reaction (2e − ‐ORR) toward hydrogen peroxide (H 2 O 2 ) suffers from sluggish O─O preservation and spin‐forbidden triplet O 2 ‐to‐singlet H 2 O 2 transition. Herein, we resolve this pivotal challenge by leveraging the chirality‐induced spin selectivity (CISS) effect in inherently chiral Salen covalent organic frameworks (C‐Salen‐COFs‐Zn) as 2e − ‐ORR electrocatalysts. The CISS effect imparts uniform surface electron spin polarization to the C‐Salen‐COFs‐Zn, whereby triplet O 2 bearing two parallel‐spin electrons readily accepts opposite‐spin electrons, alleviating the spin‐forbidden transition to promote the generation of H 2 O 2 . The C‐Salen‐COF‐Zn exhibits exceptional spin selectivity with CISS‐induced spin polarization efficiency exceeding 90%, delivering superior electrocatalytic performance to its achiral counterpart. C‐Salen‐COF‐Zn achieves 87.0% H 2 O 2 selectivity, 297.7 mmol g −1 h −1 production rates at 0.2 V versus RHE, and Faradaic efficiencies up to 93.7% at 0.6 V versus RHE in H‐type cell. Flow‐cell system achieves 1169.7 and 1207.6 mmol g −1 h −1 H 2 O 2 yield for C‐Salen‐COF‐Zn. Comprehensive mechanistic studies reveal that C‐Salen‐COF‐Zn preferentially adopts a Pauling‐type adsorption mode, favoring •O 2 − formation by partially filling the π* antibonding orbitals, preserving the O─O bond. The spin‐selective C‐Salen‐COF‐Zn was integrated into a closed‐loop cascade system for on‐demand H 2 O 2 generation and utilization, delivering 72% sodium perborate, 56% sodium peroxycarbonate, 82.7% lignin‐to‐benzoic acid conversions, and electro‐Fenton degradation in advanced oxidation processes.

In Situ Embedded Catalytic Sites Accelerate Redox Kinetics for High‐Performance Sodium–Sulfur Batteries

ABSTRACT Sodium–sulfur (Na–S) batteries are hindered by sluggish sulfur conversion kinetics and polysulfides dissolution. Although catalysts are widely introduced to improve kinetics, the crucial question persists in how catalytic sites can be effectively accessible to polysulfides especially when pursuing a highly confined sulfur redox pathway. Here we bring catalyst accessibility into focus and demonstrate that a synthetic strategy based on in situ embedded catalytic sites maximizes catalytic accessibility and efficiency. Through a bottom‐up, precursor‐integrated host synthesis route, we in situ embedded Nb 2 O 5 catalyst into carbon nanotubes in parallel with formation of extensive nanoporosity. Subsequent sulfur impregnation yields a cathode structure (I‐Nb 2 O 5 @C–S) featuring abundant catalyst–pore–sulfur triple‐phase interfaces. As a result, I‐Nb 2 O 5 @C−S delivers among the most promising sulfur utilization in literature, achieving 1540 mAh g −1 at 0.1 C, and 1044 mAh g −1 at 3 C with a low‐capacity decay of 0.027% per cycle over 1500 cycles. In contrast, a counterpart with spatially isolated Nb 2 O 5 and sulfur exhibits deficient catalytic accessibility and negligible improvement in sulfur redox kinetics. Kinetic diagnostics, combined with niobium K‐edge and operando sulfur K‐edge x‐ray absorption spectroscopy, reveal that direct accessibility of catalytic sites to sulfur is essential for synergizing polysulfide confinement and kinetic improvement.

Donor‐Glycolated Quinoidal Polymers Enable Fast N‐Type Organic Electrochemical Transistors

ABSTRACT Fast, stable n‐type organic mixed ionic‐electronic conductors remain scarce. We report a donor glycolated, quinoidal design that facilitates efficient n‐doping and spatially separates hydrophilic side chains from n‐doping sites to preserve electronic pathways. The resulting polymer PQ‐gT, synthesized from a glycolated bithiophene donor and a quinoidal bifuran‐dione acceptor, exhibits high mixed conduction with a figure of merit of µC * = 10.9 F cm −1 V −1 s −1 . In planar accumulation‐mode organic electrochemical transistors (OECTs), it exhibits nearly symmetric sub‐millisecond transients with switching on‐ and off‐times of τ on / τ off = 0.5/0.2 ms. These values represent the fastest operation for this type of device architecture. Partial donor replacement with dialkoxybithiazole tunes packing and suppresses swelling, raising µC * to 21.5 F cm −1 V −1 s −1 at 25% substitution, albeit with slower switching. In vertical OECTs, PQ‐gT supports balanced ambipolar operation with ∼1 ms switching and enables a single‐material complementary inverter (gain ≈ 40 V V −1 at V IN < 100 mV) that is stable over 10 000 cycles and functional up to 200 Hz. This donor‐glycolated quinoidal strategy furnishes intrinsically fast, aqueous‐stable n‐type organic mixed ionic‐electronic conductors for bioelectronic circuits.

Photopatternable and Stretchable Random Polymer Semiconductor via Oxetane Side‐Chain Engineering

ABSTRACT Flexible electronic devices demand semiconducting materials that combine high charge transport performance, mechanical resilience, and compatibility with advanced patterning techniques. Conventional photolithography is incompatible with polymer semiconductors, and existing photo‐crosslinking strategies often compromise mobility due to backbone side reactions. Here we report an oxetane side‑chain engineering strategy that enables a diketopyrrolopyrrole (DPP)‑based random terpolymer, PDPPSe‑oxe17 , to form robust crosslinked networks under mild UV irradiation with iodonium salt photoinitiators. Controlled incorporation of oxetane groups (17 mol%) preserves the electronic structure of the conjugated backbone while enabling rapid ring‑opening polymerization for high‑resolution photopatterning. The polymer exhibits a high hole mobility of 2.19 ± 0.28 cm 2 V − 1 s − 1 , which slightly increases to 2.27 ± 0.19 cm 2 V − 1 s − 1 after crosslinking—representing one of the highest mobilities reported for photopatterned OFETs. The resulting 3D polyoxetane network imparts good mechanical robustness, allowing films to withstand 108% strain and retain ∼85% and ∼76% mobility at 30% and 50% strain. Even at 100% strain, the mobility remains ∼1.4 ± 0.12 cm 2 V − 1 s − 1 , whereas non‑crosslinked counterparts retain only ∼3% of their initial mobility. This work establishes a generalizable molecular design principle for intrinsically photopatternable and stretchable polymer semiconductors.

Short Sb···Sb Contacts in Polymorphic Tris( <i>p‐</i> Tolyl)Antimony: A Hallmark of Organoantimony(III) Solid‐State Chemistry?

ABSTRACT Discovery of a polymorph of tris( p‐ tolyl)antimony(III) reveals solid‐state supramolecular dimers connected through short, attractive Sb∙∙∙Sb contacts that, based on theoretical calculations and a systematic screen of the Cambridge Structural Database (CSD), could be an overlooked hallmark of the solid‐state and supramolecular chemistry of trivalent organoantimony(III) compounds. While the previously reported crystal structure of tris( p‐ tolyl)antimony(III) is known to exhibit phenyl embrace motifs, resembling the arsenic or phosphorus analogs, the new polymorph exhibits supramolecular dimers characterized by direct Sb∙∙∙Sb contacts shorter than the sum of the van der Waals radii, and stabilized by a significant dimer dissociation energy of ca. −26 kJ mol −1 established by periodic density‐functional calculations. Theoretical analysis indicates that the contacts are attractive and dispersion‐dominated, with an overview of the CSD showing that such direct Sb···Sb contacts are not unique to this polymorphic form of tris( p‐ tolyl)antimony(III) but appear to be a more general feature of trivalent organoantimony in the solid state. Specifically, the CSD shows that dimers based on short Sb···Sb contacts are found across a number of organoantimony structures, including some of the simplest representatives of the series, such as triphenyl‐ and trimethylantimony, for which the dimer interaction energy is herein calculated to be ca. −13 kJ mol −1 .

Spatial Regulated Noncontact Ru Heterostructure for Cost‐Effective Platinum‐Free Fuel Cells

ABSTRACT Cost‐effective Ru holds tremendous promise to tackle the sluggish hydrogen oxidation reaction (HOR) kinetics. Rational spatial distribution design of heterostructure components is crucial for electrochemical reactions involving multiple intermediates, particularly in fuel cells. In this study, we demonstrate a noncontact heterostructure catalyst featuring spatially separated but functionally synergistic ruthenium (Ru) nanoparticles (NPs) and molybdenum carbide (MoC) clusters (CLs) interconnected by a conductive carbon support (Ru‐MoC/C) for the alkaline HOR. The experimental results and density functional theory (DFT) calculations demonstrate that this configuration achieves a refined division of labor and seamless collaboration in functionality through its ingenious spatial arrangement. Consequently, the Ru‐MoC/C‐based anion exchange membrane fuel cell (AEMFC) with an ultralow Ru loading of 0.05 mg Ru cm −2 and a Co 2 MnO 4 /C cathode achieves a remarkable total specific peak power of 17.4 W mg PGM −1 in H 2 ‐air, surpassing the state‐of‐the‐art catalysts. Moreover, this Pt‐free AEMFC achieves a total platinum‐group‐metal (PGM) utilization of 13.4 W mg −1 at 0.65 V, which surpassing the U.S. Department of Energy (DOE) 2025 target. Additionally, the Ru‐MoC/C‐based fuel cell can maintain stable cell operation at 0.5 A cm −2 for over 110 h. This work highlights the promise of noncontact heterostructure design in developing efficient and durable electrocatalysts and beyond.

Metal Coordination Dynamics Governs Selective Halogenation in α‐KG/Fe‐Dependent Halogenase SyrB2

ABSTRACT α‐Ketoglutarate (α‐KG)‐dependent nonheme iron enzymes catalyze a diverse array of oxidative transformations essential for natural product biosynthesis. However, the mechanism by which α‐KG/Fe‐dependent halogenases achieve selective halogenation while circumventing the thermodynamically favored hydroxylation pathway remains a subject of intense debate. In this study, we elucidate the halogenation mechanism in SyrB2 through extensive computational and crystallographic investigations. Our work reveals that metal coordination dynamics plays a pivotal role in controlling selective C─H bond activation and chlorination in SyrB2. The transformation of the Fe(IV)‐oxo species from an equatorial to an axial conformation enables hydrogen atom transfer from the substrate C─H bond. Subsequent re‐isomerization of the Fe(III)‐OH intermediate to the equatorial conformation is critical for promoting selective chlorination while minimizing competitive hydroxylation. The proposed mechanism is supported by multiple experimental observations, including Mössbauer spectroscopy, nuclear resonance vibrational spectroscopy (NRVS), 2 H‐HYSCORE spectroscopy, and kinetic analysis of reactions with various substrates.

Solvation‐Preserving Gelation of Localized High‐Concentration Electrolytes for Lithium Metal Batteries

ABSTRACT Localized high‐concentration electrolytes (LHCEs) exhibit excellent interfacial compatibility with lithium metal anodes and high‐nickel cathodes, whereas the introduction of polymer networks during gelation may alter their intrinsic solvation structures. Here, we report a solvation‐preserving gel electrolyte formed via in situ polymerization of a fluorinated polymer network within a 1,2‐Dimethoxyethane (DME)‐based LHCE. Unlike conventional gel polymer electrolytes, the fluorinated polymer exhibits limited Li + coordination, thereby largely preserving the localized high‐concentration solvation environment during gelation. This design couples the preserved LHCE solvation chemistry with a fluorinated polymer framework, enabling synergistic regulation of electrode–electrolyte interfaces and enhanced electrochemical performance. Meanwhile, the fluorinated polymer network further improves safety by reducing electrolyte flammability. Lithium symmetric cells achieve stable cycling over 2000 h, while LiNi 0.9 Co 0.05 Mn 0.05 O 2 (NCM9)|Li full cells deliver 82.2% capacity retention after 300 cycles and operate stably up to 4.5 V. At the pouch‐cell level, a gravimetric energy density of 394.3 Wh kg −1 is achieved under lean‐electrolyte conditions, while no thermal runaway is observed up to 300°C. This work demonstrates that preserving solvation structure via rational polymer network design enables simultaneous improvements in interfacial stability, safety, and practical performance in quasi‐solid‐state lithium metal batteries.

Uncaging Iridium(III) Complexes for Combined Photodynamic and Photoactivated Chemotherapy

ABSTRACT Inorganic photochemotherapy enables precise spatial and temporal control over anticancer drug activation, offering a promising strategy to reduce systemic toxicity. Two iridium(III) complexes of general formula [Ir(L)(ppy)(terpy)]PF 6 with L = N ‐acetyl‐ L ‐cysteinato methyl ester (cys) or N ‐acetyl‐ L ‐selenocysteinato methyl ester (sec), were developed as light‐activatable prodrugs with sulfur‐ and selenium‐based “caging” groups. Both complexes are stable in the dark but undergo light induced bond cleavage upon visible light activation, following distinct photochemical pathways dictated by the coordinated chalcogen. For the cys complex, an initial oxygen‐dependent formation of a sulfinato intermediate is followed by Ir─S bond cleavage. In contrast, the selenium complex first releases dehydroalanine due to Se─C bond cleavage, forming an unprecedented selenite intermediate [Ir(SeO 3 )(ppy)(terpy)], which was characterized by single crystal x‐ray diffraction. The photoactivation leads to high singlet oxygen production quantum yields (40%–48%), consistent with a type II photodynamic therapy (PDT) mechanism. Both complexes exhibit minimal dark toxicity (EC 50  &gt; 150 µM) but potent photocytotoxicity in A549 cells under blue and green light photoactivation (460 and 520 nm). This new class of photocaged iridium(III) pro‐sensitizer shows promise for combined PACT/PDT applications and demonstrates how chalcogen coordination modulates the photoreactivity and therapeutic efficacy of metal complexes.

Adsorption‐Engineered Hydrocarbon Ionomers for Durable Proton‐Exchange Membrane Fuel Cells

ABSTRACT Reducing reliance on perfluoroalkyl substances (PFAS) in proton‐exchange membrane fuel cells requires hydrocarbon ionomers that combine high performance with long‐term durability, a persistent challenge in catalyst‐layer design. Here, we identify oxidation‐driven ionomer‐catalyst interfacial degradation as a dominant failure pathway in hydrocarbon ionomer‐bonded cathodes and introduce an adsorption‐engineering strategy to overcome this limitation. The comparison of a commercial sulfonated poly(phenylene) (Pemion) with structurally engineered sulfonated poly(fluorene)s demonstrated that electrode durability is governed by the interplay between ionomer adsorption strength and resistance to oxidative degradation on carbon‐supported Pt catalysts. A poly(fluorene) ionomer with mobile alkyl sulfonic acid groups forms resilient interfaces, delivering 1.28 A cm − 2 at 0.65 V under fully humidified H 2 /air conditions (80°C and 150 kPa abs ), comparable to Pemion. After 90,000 accelerated potential cycles, the poly(fluorene)‐bonded cathode exhibits significantly improved durability, with only 29% performance loss compared to 58% for Pemion; further molecular refinement reduces the loss to 17%, approaching that of Nafion‐bonded cathodes (14%). These findings establish adsorption‐engineered ionomer design that decouples interfacial anchoring from oxidative degradation as a general strategy for achieving durable, high‐performance PFAS‐free PEM fuel cell electrodes.

Carlos M. Cruz