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Oxygen‐Tolerant Photo‐Induced Miniaturized Accelerated Atom Transfer Radical Polymerization (OPTIMA‐ATRP) for High‐Throughput Synthesis of Polymer Bioconjugates
ABSTRACT Conjugates of synthetic polymers with biomolecules, forming polymer bioconjugates (PBCs), are used to improve the pharmacokinetic properties of many biological therapeutics. Growing synthetic polymers from biomolecules via reversible deactivation radical polymerization (RDRP) demonstrated enormous potential as an alternative to the “grafting to” method in synthesizing biohybrids. However, conventional “grafting from” approaches applied to biomolecules are hindered by large reaction volumes, long reaction times, rigorous deoxygenation, and complex workflows, rendering them unsuitable for synthesizing libraries of PBCs needed to collect large data sets for emerging materials discovery. Herein, Oxygen‐tolerant photo‐induced miniaturized accelerated atom transfer radical polymerization (OPTIMA‐ATRP) in water was developed for the polymerization of hydrophilic (meth)acrylate monomers under ambient or sub‐ambient (4°C) temperature and atmospheric conditions, without prior degassing, in < 10 min. Sodium pyruvate (SP) in conjunction with UV light (380–395 nm, 28.5–30 mW/cm 2 ) promoted rapid controlled polymerization in water, on an ultra‐small scale (< 50 µL) in micropipette tips or 96‐well plate. By exploiting this OPTIMA‐ATRP, cost‐effective syntheses of several types of PBCs (e.g., DNA‐, peptide‐, lipid‐, and protein–polymer hybrids) were carried out using a parallel, high‐throughput approach. This technique enables rapid optimization of biohybrid synthesis, previously inaccessible under conventional conditions, and empowers non‐specialists to use ATRP in various areas.
Boosting Both Chemical and Electrochemical Tandem Steps in Low‐Potential Aldehyde Oxidation for Solar‐Driven Bipolar Hydrogen Production
ABSTRACT Low‐potential aldehyde oxidation offers an energy‐efficient anodic alternative to oxygen evolution for bipolar hydrogen production coupled with biomass valorization, yet the tandem non‐Faradaic/Faradaic mechanism remains poorly understood. Here, we report PtCu 3 ‐coated Cu nanowire arrays supported on Cu foam (PtCu 3 @Cu/CF) fabricated via galvanic replacement and electrochemical reduction. In situ ATR‐FTIR and DFT calculations indicate the PtCu 3 shell enhances adsorption of the gem ‐diolate intermediate while weakens binding of 5‐hydroxymethyl‐2‐furancarboxylic acid (HMFCA), accelerating both non‐Faradaic C–H cleavage and Faradaic oxidation. This enables selective 5‐hydroxymethylfurfural upgrading with anodic hydrogen evolution at 300 mA cm −2 at ∼0.21 V in a two‐electrode flow electrolyzer. Additionally, the electrolyzer also achieves 100 mA cm −2 at 0.16 V with 200% combined Faradaic efficiency for bipolar hydrogen production. Integration of a six‐cell stack with perovskite photovoltaic module yields a bias‐free solar‐to‐hydrogen efficiency of 16.9% alongside gram‐scale HMFCA production. This noble‐metal‐lean platform establishes scalable solar reforming for co‐generating green hydrogen and value‐added chemicals.
Spatial Molecular Decoupling Design for High‐Z and Fast Organic Scintillators
ABSTRACT Organic scintillators are pivotal for flexible and low‐cost radiation detection; however, they face a long‐standing “absorption–speed” trade‐off: incorporating high‐Z elements to enhance X‐ray attenuation typically triggers strong spin–orbit coupling (SOC), which quenches prompt fluorescence and diverts excitation energy into slow, microsecond‐scale triplet pathways. Here, we present a molecular decoupling strategy to overcome this dilemma, realized in a donor–acceptor–donor (D–A–D) hybridized local and charge‐transfer (HLCT) molecule, 4,7‐bis(4‐(bis(4‐iodophenyl)methyl)phenyl)benzo[ c ][1,2,5]thiadiazole (TPBI). By terminally tethering iodine atoms to the triphenylamine units, we achieve robust X‐ray attenuation while preserving a fast “hot‐exciton” emission channel. The intrinsic nonplanar geometry and strategic spatial arrangement of the molecule successfully isolate the heavy‐atom effect from the emissive core, maintaining the crucial quasi‐degeneracy between the T 2 and S 1 states. This configuration facilitates rapid high‐lying reverse intersystem crossing (hRISC), enabling near‐unity exciton utilization without compromising nanosecond‐scale decay kinetics. Our TPBI‐based scintillator demonstrates a synergized performance profile of potent X‐ray interaction (attenuation efficiency 5.672 cm 2 g −1 at 28 keV) and a fast temporal response (2.96 ns), providing a general molecular design paradigm for next‐generation, high‐performance organic radiation detectors.
Cage‐Type Porous Organic Salts as Ship‐in‐a‐Bottle Nanoreactors for Light‐Transparent and Reusable Molecular Photocatalysts
ABSTRACT Heterogenizing molecular photocatalysts while preserving their intact, pre‐designed structures—without redesigning the host—remains a fundamental challenge. Immobilization within porous materials offers control over reaction environments and improved recyclability; however, most host systems require catalyst‐specific structural redesign, limiting generality. We introduce a cage‐type porous organic salt (POS) as a modular host platform for homogeneous, molecularly defined photocatalysts (organic molecules and metal coordination complexes) based on a ship‐in‐a‐bottle strategy. A sodalite‐type POS constructed from adamantane‐based sulfonic acid and tri(ethynylphenyl)methylamine provides well‐defined, light‐transparent, cage‐like internal cavities. Single‐crystal X‐ray diffraction reveals that the POS accommodates diverse photocatalysts, including anthraquinone, phenanthrenequinone, and phthalocyanine, through a unified recrystallization protocol. The framework exhibits negligible absorption in the visible region, enabling selective excitation of photocatalysts without competitive light absorption. Post‐synthetic thiol–yne crosslinking of ethynyl groups on the pore surface reinforces the framework and renders it insoluble while preserving cage‐like cavities. For example, a phenanthrenequinone‐encapsulated POS functions as a reusable heterogeneous photocatalyst for visible‐light‐driven hydrogen peroxide production from isopropanol and oxygen, achieving rates of up to 4.2 mmol g −1 h −1 without catalyst leaching. Overall, cage‐type POSs serve as light‐transparent nanoreactors for intact molecular photocatalysts, providing a modular, expandable platform for photocatalyst immobilization and post‐synthetic functionalization.
Lattice Oxygen Engineering in Ni–Co Hydroxides for Efficient Methanol Oxidation Coupled With Hydrogen Production
ABSTRACT Electrocatalytic methanol oxidation reaction (MOR) coupled with hydrogen evolution (HER) can lower the energy cost of H 2 production while valorizing methanol to formate. Developing efficient, low‐cost MOR catalysts for alkaline media remains challenging. Here, we report nickel–cobalt bimetal hydroxide (NiCoO x H y ) nanosheets as a highly active and durable MOR catalysts. The optimized NiCoO x H y requires only 1.40 V versus the reversible hydrogen electrode (RHE) to deliver a current density of 400 mA cm −2 and achieves >99% Faradaic efficiency toward formate at 1.45 V, representing one of the most efficient MOR electrocatalysts reported. In a two‐electrode system, methanol oxidation coupled with HER lowers the cell voltage by ∼310 mV compared to conventional water electrolysis at 300 mA cm −2 . In situ Raman and x‐ray absorption spectroscopy, together with isotope‐labeling studies, reveal that cobalt incorporation promotes the formation of high‐valence M 4+ species, which activate lattice oxygen and accelerate methanol electrooxidation. Density functional theory (DFT) calculations confirm that highly oxidized M 4+ species enhance metal–oxygen orbital hybridization, activating lattice oxygen and reducing reaction barriers. This work highlights lattice oxygen engineering via electronic structure modulation as an effective strategy for designing advanced electrocatalysts toward sustainable hydrogen‐formate co‐production.
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.