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Surface Charge Regulated Non‐Equilibrium Assembly and Open Living Crystals of Chemically Driven Ring‐Shaped Micromotors
ABSTRACT Active colloidal systems, driven by self‐propulsion and collective dynamics, offer a non‐equilibrium route to soft materials. Realizing such materials hinges on creating novel active systems and deciphering their collective behavior. Here we present a new type of ring‐shaped, partially‐coated Pt‐SiO 2 colloidal micromotor and report our finding that the sign of the surface charge plays a crucial role in determining the propulsion speed and reversing the living crystallization behavior. Our results show that negatively charged ring‐shaped micromotors can achieve high propulsion speeds exceeding 20 µm s − 1 at 0.5 wt% H 2 O 2 solution, whereas positively charged rings move much more slowly. We further find that negatively and positively charged rings always exhibit opposite living crystallization behaviors: if one type can crystallize, the other cannot. We reveal that this opposite crystallization behavior stems from the consistently opposite EO flow directions, irrespective of whether the flow field is symmetric or asymmetric. Living crystallization occurs only when the inward EO flow region exceeds 50% of the ring circumference. By combining experiments and numerical simulations, we demonstrate that the sharp difference in the flow fields between oppositely charged ring‐shaped micromotors originates from the different surface charge signs of the rings and the substrate.
Extending Chain Length of PNP Pincer Ligands Triggers Catalytic Activity of Gold–Copper Nanoclusters in Aerobic Oxidations
ABSTRACT Structural isomerism of organic ligand‐protected atomically precise metal nanoclusters constitutes an ideal model for revealing the structure–activity relationship of nano‐catalysts at the atomic level, while purposefully designing and synthesizing catalytically active metal nanocluster structural isomers remains a central challenge. Herein, we developed a generalizable strategy toward the construction of isomeric metal nanoclusters by varying the chain length of PNP pincer ligands. A pair of metal nanocluster structural isomers 2C‐Au 10 Cu 6 and 3C‐Au 10 Cu 6 has been successfully synthesized and crystallographically characterized. The structural isomerism phenomenon originating from one atomic Au/Cu shuttle in the kernel and the resulted surface ligand arrangement was uncovered at the atomic level based on their precise structures. The structural isomerism leads to the significantly different electron transfer and surface activation ability of 2C‐Au 10 Cu 6 and 3C‐Au 10 Cu 6 , thus triggering the superior activity of 3C‐Au 10 Cu 6 in catalyzing aerobic oxidations. This work would be enlightening for precisely regulating the metal kernel and surface structures of metal nanoclusters for efficient catalysis, and also be inspiring for the rational design of metal nanocluster structural isomers.
Cross‐linked Ion‐Pair Microporous Polymers Enabling Durable High‐Temperature Proton Exchange Membrane Fuel Cells
ABSTRACT Phosphoric acid (PA)‐doped ion‐pair polymers have emerged as promising proton exchange membranes (PEMs) for high‐temperature fuel cells, enabling operation from 80°C–160°C while effectively anchoring and retaining PA. However, conventional ion‐pair‐based PEM fuel cells suffer from performance degradation and unstable proton transport at temperatures above 160°C. In this study, a cross‐linked ion‐pair microporous polymer, poly(spirobisindane‐co‐terphenyl piperidinium) (C50‐PSTP‐x), is simultaneously used as both the PEM and catalyst‐layer ionomer, achieving a strong acid anchoring effect across the entire membrane electrode assembly. The polymer integrates ion‐pair‐coordinated PA‐cyclic quaternary ammonium groups, a spirobisindane backbone with intrinsic microporosity, and a highly roughened cross‐linked structure. These structural features collectively promote efficient proton transport, well‐defined triple‐phase interfaces, and strong PA anchoring, enabling stable fuel cell operation at temperatures up to 220°C. C50‐PSTP‐x membrane and ionomer deliver high peak power densities of 0.680–0.778 W cm −2 with a Pt loading of 0.5 mg Pt cm −2 , along with excellent durability, exhibiting low voltage decay rate of 57.8 µV h −1 over 800 h at 160°C and 33.3 µV h −1 over 500 h at 180°C. This work establishes a robust ion‐pair polymer platform for ultra‐high‐temperature PEM fuel cells (HT‐PEMFCs), expanding both the operational temperature window and long‐term stability of next‐generation HT‐PEMFCs.
Downsizing the Histone H3–H4 Quaternary Structure Into Foldamer Mimetics Yields High‐Affinity and Cell‐Permeable Ligands of ASF1
ABSTRACT Mimicking complex protein–protein interfaces with small, well‐defined molecular scaffolds remains a major challenge in chemical biology. Here, we report a foldamer‐based downsizing strategy that compresses the quaternary architecture of the histone H3–H4 dimer into compact peptide‐oligourea hybrids acting as high‐affinity ligands of the histone chaperone Anti‐Silencing Function 1 (ASF1). Guided by multiple high‐resolution co‐crystal structures, we designed a series of foldamer mimetics that accurately reproduce both the H3 α‐helix and the H4 β‐strand epitopes. Systematic optimization of linker geometry, β‐strand mimicry, formal charge, and selective backbone N‐methylation yielded highly stable ligands with nanomolar affinities, enhanced proteolytic resistance, and robust cytosolic penetration. Notably, the optimized constructs and their N‐methylated analogues recapitulate the binding mode of the native H3–H4 dimer on ASF1 with high fidelity and engage endogenous ASF1 in cell extracts, demonstrating effective intracellular target recognition. Together, these results show that peptide‐oligourea foldamers can reproduce the structural features of a protein quaternary structure surface, combining high affinity, high stability and cell permeability.
Giant Light‐Heat‐Electricity Conversion in Photothermoelectric Detector Enabled by Semiconductor‐Dielectric Superlattices
ABSTRACT Photothermoelectric (PTE) detectors, which operate relying on the photothermal and thermoelectric effects, can overcome the intrinsic spectral limitations originated from material bandgaps in photon‐driven detectors. However, the hardware implementation of devices leveraging light‐heat‐electricity cascade conversion remains challenging. Here, we report the construction of MoS 2 /SiO 2 semiconductor/dielectric superlattice films with features of nanoscale layer definition, high crystalline quality, and wafer‐level manufacturability. Benefiting from the interlayer interference and electric‐field localization, the MoS 2 /SiO 2 superlattices exhibit remarkably enhanced optical absorption across the visible to infrared spectrum, which enables the high photothermal energy conversion efficiency and substantial temperature rise exceeding 70 K. The PTE detection, implemented by integrating superlattice absorber with a microscale thermoelectric (μ‐TE) platform based on Bi 2 Te 3 /Sb 2 Te 3 P–N pairs, enables high‐efficiency photodetection through strong light–matter interaction and optimized thermal management. The self‐powered detector can stably operate over a broad‐spectrum range extending to 1550 nm, demonstrating a temporal response (∼16 ms), high responsivity (17.6 V W −1 ), and detectivity exceeding 1.20 × 10 10 Jones, comparable to state‐of‐the‐art broadband PTE detectors. Array‐level integration facilitates high‐fidelity 1550 nm imaging with a 256‐pixel prototype, while wafer‐scale fabrication of over 3000 units on a 2‐inch substrate confirms excellent uniformity, reproducibility and scalability, unlocking the potential for advanced large‐scale imaging applications.
Step‐Associated Cu‐Ceria Interfaces Enhance Catalytic Activity and Selectivity
ABSTRACT Precise control of metal–support interactions is essential for understanding and steering catalytic processes. Here, we demonstrate that the surface location of metal nanoparticles (NPs) on oxide supports can strongly influence catalytic performance. Using atom‐trapped Cu catalysts as precursors enabled the formation of Cu NPs with distinct Cu–CeO 2 interfacial environments compared with catalysts prepared by impregnation or colloidal methods. These resulting catalysts exhibit enhanced CO 2 hydrogenation toward methanol formation by promoting formate activation. Enhanced reactivity arises from these Cu–CeO 2 interfacial environments that render the methanol formation pathway thermodynamically more favorable, as revealed by theoretical calculations. These findings provide mechanistic insights into how NP anchoring environments influence catalytic activity and selectivity, offering a rational design strategy for oxide‐supported metal catalysts.
A Self‐Phase‐Separated Deep Eutectic Solvent‐Based Biphasic Electrolyte for Durable Four‐Electron Zn‐I <sub>2</sub> Batteries Across Wide‐Temperature Range
ABSTRACT Aqueous four‐electron zinc‐iodine batteries (4eZIBs) hold great promise for long‐term energy storage, but their practical application is severely hindered by the multiple drawbacks, including Zn dendrite growth, polyiodide shuttle, and I + hydrolysis. Such limitations can be effectively mitigated by employing biphasic electrolytes featuring a liquid‐liquid interface, which enables efficient immobilization of the dissolved reaction intermediates. However, such systems frequently employ toxic organic solvents, which not only pose flammability risks but also struggle to adapt to extreme temperature conditions. Herein, we design a novel self‐stratified biphasic electrolyte via liquid‐liquid phase separation of choline chloride (ChCl)‐trifluoroacetamide (TFA) deep eutectic solvent (DES) and ZnSO 4 /H 2 O/ ethylene glycol solution. The upper DES phase effectively confines polyiodide anions, suppresses shuttle effect and stabilizes I + species, while the bottom aqueous phase regulates Zn 2+ solvation structure and inhibits dendrite formation and side reactions. Benefiting from the synergistic functional separation, the Zn‐I 2 battery realizes highly reversible four‐electron conversion, effectively suppresses battery self‐discharge, and delivers superior cycling stability over 21000 cycles as well as wide temperature tolerance ranging from −30°C to 50°C. This work offers novel insights into the design of safe and eco‐friendly biphasic electrolytes and provides an effective strategy for the construction of high‐performance 4eZIBs.
Gold Clusters With Open‐Shell Ligands: Superatom Mediated Magnetic Interaction
ABSTRACT Understanding the magnetic interactions within gold clusters that involve superatomic orbitals is critically important in advancing the development of nanoscale materials with magnetic functionality. In this study, we report on the synthesis of Ir‐doped Au 12 (Ir@Au 12 ) icosahedral clusters functionalized with two open‐shell verdazyl radicals at opposite poles, along with an investigation into their electronic, magnetic, and photophysical properties. The photoluminescence from the Ir@Au 12 cluster core is drastically quenched by the introduction of verdazyl ligands. The ultrafast time‐resolved absorption spectroscopy reveals the electron transfer from the Ir@Au 12 core in the triplet excited state to the verdazyl ligand. The EPR study discloses the hyperfine coupling with the Au and Ir nuclei, indicating the spin density of the verdazyl radical moderately delocalized over the Ir@Au 12 core. These results provide direct evidence of electronic interaction between the organic radicals and Ir@Au 12 superatomic core. Furthermore, the variable temperature EPR study suggests weak magnetic communication between the two verdazyl radical ligands mediated by the Ir@Au 12 superatomic core. These findings will establish superatom–organic radical hybrids as a new class of multi‐spin systems and provide a design strategy for photofunctional and magnetic nanomaterials based on atomically precise metal clusters.
A Universal van der Waals Tunneling Injector for Monolayer CMOS
ABSTRACT Two‐dimensional (2D) semiconductors are poised to extend logic technology to the atomic‐thickness limit, yet monolayer complementary metal‐oxide‐semiconductor (CMOS) has been largely hampered by polarity‐dependent, thermionic‐emission‐dominated contacts that preclude a unified injection solution. Here, we introduce degenerately doped, crystalline SnSe 2 as a universal source‐side van der Waals (vdW) injector capable of enforcing all‐tunneling carrier injection into both p ‐ and n ‐type monolayer channels. The combination of a large electron affinity (∼5.1 eV), degenerate carrier density (>10 19 cm −3 ), and atomically uniform vdW interfacial coupling enables polarity‐tailored tunneling mechanisms while effectively suppressing interfacial gap states. In p ‐type WSe 2 , a type‐III (broken gap) alignment drives efficient band‐to‐band tunneling, yielding a >1000‐fold enhancement in drive current over conventional metal electrodes. In n ‐type MoS 2 , the SnSe 2 injector forms a type‐I heterojunction within the sub‐depletion‐width monolayer body, enabling a gate‐tunable injection that evolves from field‐controlled Fowler–Nordheim‐like tunneling to thickness‐limited tunneling, achieving an on/off ratio > 10 9 and a subthreshold swing below 70 mV dec −1 . Integrating this single‐material injector, we demonstrate a monolayer CMOS inverter with a maximum voltage gain of ∼340 at V DD = 2 V, establishing degenerate SnSe 2 as a dual‐polarity vdW injector and providing a platform for high‐performance, low‐power 2D integrated circuits.
Oxophilic Gallium Single‐Atom Regulating Micropore‐Confined Os Atomic Clusters Enables Efficient Alkaline Hydrogen Electrocatalysis
ABSTRACT Rational design of cost‐effective atomic cluster (AC) catalysts with high mass activity and robust durability remains a formidable challenge for alkaline hydrogen‐energy conversion, owing to intrinsic aggregation of ACs, difficulty in decoupling the adsorption energetics of hydrogen‐ and oxygen‐containing intermediates, and acute CO poisoning. Herein, we report the synthesis of a class of electrocatalysts using carbon‐micropore confinement with adjacent isolated oxophilic Ga sites to stabilize Os ACs and decouple these conflicting interfacial adsorption demands. We demonstrate that carbon aerogel micropores kinetically lock ultrasmall Os clusters against migration and coalescence, while Ga sites polarize spatially proximate Os clusters through support‐mediated charge redistribution, downshifting the Os d ‐band center and weakening H* and CO* binding. Meanwhile, Lewis‐acidic oxophilic Ga centers capture and activate H 2 O/OH* species, establishing an oxygenated‐intermediate relay that lowers the barrier for the sluggish Volmer step. Os AC/Ga 1 @pCA delivers exceptional mass activities for hydrogen evolution (2185.5 A g Os −1 at 100 mV) and hydrogen oxidation (7.29 A mg Os −1 at 50 mV), together with outstanding CO tolerance. In an anion‐exchange‐membrane water‐electrolyzer, it achieves a PGM‐price‐normalized activity of 370.7 A dollar −1 at 1.8 V and operates stably at 500 mA cm −2 for over 300 h with a degradation rate of mere ∼48.6 µV h −1 .
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.