Browse Articles

Twisted Intramolecular Charge Shuttle (TICS) Enables Ultrafast Ratiometric Sensing and Imaging of Nitrite

ABSTRACT Ratiometric fluorescence sensing offers superior interference resistance and self‐calibration, yet designing these probes remains challenging due to a lack of generalizable mechanisms. Herein, we introduce a novel, mechanism‐driven strategy based on the twisted intramolecular charge shuttle (TICS) process to achieve ultrafast, sensitive nitrite (NO 2 − ) ratiometric detection. By strategically installing an o‐phenylenediamine (OPD) fragment at the reactive meso‐position of a pyronin fluorophore, we successfully induced and modulated the TICS process through a specific reaction with NO 2 − . This generates a robust ratiometric response with a remarkably low detection limit (6.6 nM) and an ultrafast response time of 18 s—two orders of magnitude faster than the classical Griess method. To demonstrate practical utility, we incorporated the probe into a portable device for rapid, visual on‐site quantification of nitrite in food and water. Furthermore, the probe successfully imaged endogenous NO 2 − dynamics in living plants, revealing a direct correlation between nitrite fluctuations and environmental stress. This study establishes TICS as a powerful platform for probe design, marking a significant transition from empirical dye screening toward rational, mechanism‐driven molecular engineering.

Dual Breaking the Geometric and Electronic Symmetry of Covalent Organic Framework for Enhanced H ₂ O ₂ Photosynthesis

ABSTRACT The efficient conversion of solar energy into chemicals is fundamentally limited by the rapid, random recombination of photogenerated charges and strong exciton binding in semiconductors. We transcend incremental catalyst optimization by introducing a universal molecular design strategy “simultaneous geometric and electronic symmetry breaking” in covalent organic frameworks that intrinsically programs directional charge flow. Our strategy of replacing symmetric benzene units with asymmetric thiophene rings induces cooperative point‐group distortion and asymmetric electron density redistribution, thereby creating a built‐in polarization field that slashes exciton binding energy, extends carrier lifetime by over 300%, and steers reaction selectivity. This leads to a record photocatalytic H 2 O 2 production rate from just water and air. Crucially, life‐cycle assessment confirms this pathway reduces environmental impact by an order of magnitude. The generality of this design strategy is further validated across multiple framework systems and enables stable operation in a continuous‐flow photoreactor, demonstrating a robust platform for efficient solar‐to‐chemical energy conversion.

Edge Sulfur Vacancies on MoS ₂ Enable Room‐Temperature Hydrodeoxygenation of 5‐Hydroxymethylfurfural

ABSTRACT Selective hydrodeoxygenation (HDO) of biomass‐derived platform molecule 5‐hydroxymethylfurfural (HMF) to synthetic chemicals and liquid biofuels with high activity and selectivity is attractive yet challenging, especially at low temperature. Herein, we report a highly active and selective MoS 2 catalyst (denoted as MoS 2 ‐T) enriched with edge sulfur vacancies by using a modified hard template method, which displays a high yield of 97.2% toward C6 fuel blend (mixture of 2,5‐dimethylfuran (DMF) and 1,2‐bis(5‐methyl‐2‐furanyl)ethylene (BMFE)) in the HDO of HMF at 70°C. In particular, the activity of HMF conversion could be reached up to 100% with prolonged reaction time even at room temperature. A combination of H‐D exchange, KIE experiments, and density function theory studies indicates that the abundant edge sulfur vacancies on MoS 2 ‐T facilitate the activation and dissociation of H 2 as well as the cleavage of C─O bonds, thus accounting for the high activity of HMF conversion at near‐ambient‐temperature. The vacancy engineering strategy developed in this work offers a new approach for designing efficient, low‐cost non‐noble metal catalysts for producing furan‐based fuels from biomass.

CO ₂ ‐Induced Reverse Lattice Oxygen Spillover on Pt/CeO ₂ Enables Sulfur‐Resistant Dry Reforming of Methane

ABSTRACT Overcoming sulfur poisoning in dry reforming of methane (DRM), which is a critical process for biogas upgrading, is particularly challenging. In this study, we illustrate that a reverse lattice oxygen spillover (RLOS) from CeO 2 to Pt on the Pt‐O‐Ce interface, induced by CO 2 , can oxidize S into SO 2 , aiding in the removal of S deposits. A low oxygen migration barrier at the Pt–O–Ce interface and Pt's high activity for oxidizing sulfur to SO 2 make Pt/CeO 2 uniquely effective at self‐recovering after H 2 S poisoning. Furthermore, the atomically dispersed Pt/CeO 2 catalyst undergoes reaction driven adaptive restructuring, which amplifies the RLOS effect and enables dynamic S deposition and removal. As a result, the catalysts maintain constant DRM activity for 100 h, even in the presence of H 2 S. This discovery paves the way for designing catalysts that resist sulfur poisoning in H 2 S‐containing streams.

Light‐Promoted Efficient Gold Recovery Enabled by a Polydopamine‐Functionalized Covalent Organic Framework

ABSTRACT The rapid proliferation of artificial intelligence (AI) and information technologies is driving a sharp increase in global electronic waste, creating an urgent demand for recovering precious metals like gold from secondary resources to achieve environmental and economic benefits. Herein, a polydopamine (PDA)‐functionalized β‐ketoenamine‐linked covalent organic framework composite, denoted as TATP/PDA, is designed in combination with a light‐assisted strategy for efficient gold recovery. Benefiting from the synergistic effects of hydrogen bonding and π‐π interactions between PDA and the TATP COF, which enhance photoelectric activity and provide abundant adsorption sites, the TATP/PDA exhibits an exceptional adsorption capacity of 5220 mg·g −1 , ultrafast adsorption kinetics (>99% removal efficiency within 30 s), and remarkable selectivity in complex matrices. Experimental characterizations disclose that the engineered abundant nitrogen and oxygen active sites, along with the inherent photocatalytic reduction capability, significantly enhance the gold adsorption performance. These key merits position TATP/PDA as one of the best‐performing materials in terms of overall performance. In practical application, TATP/PDA exhibits exceptional performance in recovering gold from real e‐waste leachate. Moreover, the recovered gold‐loaded composite serves as a sustainable photocatalyst for hydrogen evolution. This dual‐benefit strategy not only promotes resource recycling but also contributes to the goals of a green and circular economy.

Shielding Co ₃ O ₄ by Inert Carbonized Polymer Dots Enables Chlorine Resistance Toward Durable Ampere‐Level Oxygen Evolution

ABSTRACT Seawater electrolysis is crucial for large‐scale green hydrogen production, yet high concentrations of chloride ions (Cl − ) result in competitive adsorption, leading to severe catalyst degradation and electrode corrosion. To address this challenge, we develop a Co 3 O 4 @carbonized polymer dots (CPDs) electrocatalyst, which achieves a low overpotential of 270 mV at 500 mA cm −2 , together with outstanding durability of 4200 h at 600 mA cm −2 and 3200 h at 800 mA cm −2 . An anion exchange membrane simulated‐seawater electrolyzer (AEMSE) based on Co 3 O 4 @CPDs achieves stable seawater electrolysis for over 1500 h at 1.0 A cm −2 with a very low cell voltage of 1.73 V. The combined experimental and theoretical studies reveal that CPDs stabilize the lattice oxygen and decrease the reaction energy barrier, thereby switching the lattice oxygen‐mediated mechanism (LOM) pathway to more desired adsorbate evolution mechanism (AEM). Furthermore, surface‐anchored CPDs generate CO 3 2− through electro‐oxidation, forming a protection system that blocks Cl − adsorption and penetration. This strategy successfully overcomes the corrosion bottleneck in seawater electrolysis and opens new avenues for sustainable hydrogen energy development.

Solid‐to‐Solid Zn Anode and Interhalogen Iodine Cathodes for High‐Voltage Fluoride‐Ion Batteries

ABSTRACT Fluoride ion batteries (FIBs) operated at room temperature typically suffer from low output voltages (< 0.5 V) due to the lack of reversible, suitable electrode chemistries in liquid electrolytes. Here, we report a high‐voltage aqueous FIB system delivering an output voltage of ∼1.3 V by coupling a zinc/zinc hydroxyfluoride (Zn↔ZnOHF) anode with an iodine cathode undergoing reversible I − ↔I 2 F − interhalogen conversion in an NH 4 F‐based methanol/water hybrid electrolyte. At the anode, strong complexation between NH 4 + and Zn 2+ activates a reversible solid‐to‐solid Zn↔ZnOHF conversion. Meanwhile, methanol effectively suppresses HER and accelerates fluoride‐ion desolvation, leading to fast kinetics and high reversibility. As a result, the ZnOHF/Zn anode exhibits remarkable durability for over 1100 h at 1 mA cm −2 and 2 mAh cm −2 . At the cathode, tetrahexylammonium iodide (THAI) induces the formation of insoluble THAI 2 F during the fluorination of I 2 cathode, effectively immobilizing iodine species and suppressing shuttle effects. The proposed fluoride‐ion‐shuttled Zn/I 2 cells deliver a high specific capacity of 168 mAh g −1 at 2 A g −1 and retain 81% capacity after 2500 cycles. This work establishes interhalogen chemistry and electrolyte‐regulated solid‐state fluorination as viable strategies for designing high‐voltage, long‐life FIBs.

Interstitial C/N Doping Stabilizes Pd@Pt Core–Shell Electrocatalysts by Atomic‐Scale Interfacial Anchoring and Metal Dissolution Suppression

ABSTRACT Platinum (Pt)‐based multimetallic catalysts, including alloys and core–shell architectures, have attracted widespread attention due to their ability to optimize catalytic activity and minimize the use of precious metals. However, their structural instability under harsh electrochemical conditions, such as acidic media and high potentials, hinders commercialization. Here, using well‐defined Pd@Pt core–shell nanocrystals as a model system and combining online dissolution analysis (SFC‐ICP‐MS), identical‐location STEM, operando x‐ray absorption spectroscopy, and DFT calculations, we identified a pinhole‐mediated dissolution mechanism. Specifically, Pd dissolution at pinhole defects disrupts the local interfacial structure, subsequently destabilizing neighboring Pt and leading to irreversible reconstruction of the core–shell architecture, ultimately resulting in shell collapse. We further demonstrated that interstitial C/N doping at the Pd–Pt interface near pinholes could induce atomic‐scale interfacial anchoring through strong p–d hybridization, thereby significantly increasing the kinetic barrier for metal leaching. Consequently, compared to the undoped sample, the C/N‐doped core–shell catalyst maintained structural integrity at potentials up to 1.50 V (vs RHE), and the dissolution of Pt and Pd was reduced by 48.5 and 13.9 times, respectively. This defect‐targeted strengthening strategy, applicable to Pd–Au and Pd–Ag systems, establishes a general principle for stabilizing multimetallic heterointerfaces and developing durable, low‐Pt electrocatalysts.

Modulating Solvation Structure and Electrical Double Layer via Anion‐Additive Weak Interactions for High‐Voltage Lithium Metal Batteries

ABSTRACT High‐voltage lithium metal batteries have attracted attention due to their exceptional energy density. However, their practical deployment is impeded by the instability of the electrode‐electrolyte interface (EEI). Here, we report a strategy to construct a mechanically robust yet flexible EEI by synergistically regulating the solvation structure and electrical double layer (EDL) via weak interactions between DFOB − and the 2‐thiophenecarbonitrile (2‐TC) additive in weakly solvating electrolytes. Specifically, the ion‐dipole interactions between strongly solvating 2‐TC and DFOB − facilitate DFOB − ‐rich contact ion pairs and aggregate structures. Concurrently, preferential co‐adsorption of 2‐TC/DFOB − at the cathode surface synergizes with intermolecular weak interactions to reconfigure the EDL into a DFOB − ‐enriched and solvent‐deficient architecture. This synergistic modulation of the solvation sheath and interfacial EDL facilitates the formation of LiF/LiB x O y ‐rich EEI. Furthermore, electric field‐induced in situ polymerization of 2‐TC generates a flexible polythiophene network, endowing the EEI with exceptional volume strain tolerance. This electrolyte enables Li||NCM811 battery to deliver stable cycling over a wide temperature range (−20°C to 60°C) and at a high voltage of 4.7 V. Furthermore, practical 4.8 Ah Li||NCM90 and 4.4 Ah Li||LiCoO 2 pouch cells with this electrolyte achieve energy densities of 472 Wh kg −1 and 429 Wh kg −1 , respectively, while maintaining stable cycling performance.

Chemically Circular Poly(Orthoester) Elastomers Synthesized by Halogen‐Bond Donor Catalyzed Cationic Ring‐Opening Polymerization

ABSTRACT Synthetic polymers are essential to modern life, yet their large‐scale production and environmental accumulation necessitate the development of more sustainable alternatives. Existing synthetic approaches to next‐generation polymers largely focus on well‐established monomer classes, yet developing methodologies for the polymerization of underexplored functionalities would unlock challenging‐to‐access polymer classes and exploration of uncharted materials space. Poly(orthoesters) are an underexplored class of biodegradable and chemically recyclable polymers, and here we overcome long‐standing synthetic challenges by developing a molecular weight‐controlled synthesis via cationic ring‐opening polymerization of spiro orthoesters. Polymerization control is imparted by a tridentate halogen‐bond donor catalyst that selectively promotes reversible‐deactivation via anion‐binding, while suppressing undesired monomer activation. Mechanistic studies reveal that precise molecular weight control is maintained despite termination events, constituting a rare example of a polymerization exhibiting immortal‐like behavior. Combined with controlled degradation, chemical recycling to monomer, and tunable material properties, this work establishes poly(orthoesters) as a promising platform for sustainable and circular materials.

Evidence for Spin Polarization and Lattice Oxygen Migration During Cyclohexane Oxidation Over CoO _x /Fe ₂ O ₃

ABSTRACT The selective aerobic oxidation of alkanes plays a pivotal role in the sustainable conversion of hydrocarbons. However, designing catalysts that facilitate the selective generation of radicals while avoiding side reactions (such as over‐oxidation) remains a major challenge. Herein, we demonstrate the enhanced spin polarization and lattice oxygen migration on CoO x /Fe 2 O 3 catalyst for cyclohexane oxidation under solvent‐free conditions. We introduce highly dispersed CoO x clusters on iron oxide nanorods (Co/FeNR) through atomic layer deposition, forming interfacial Co–O–Fe active sites. The high‐spin Co atoms modulate the spin‐state of neighboring Fe atoms via double‐exchange interaction, promoting the adsorption and dissociation of triplet molecular oxygen. Meanwhile, Co effectively enhances the mobility of lattice oxygen, further forming the interface‐confined radical intermediate. Both spin polarization‐promoted oxygen activation and lattice oxygen migration drive the transformation of interface‐confined radicals, thus suppressing side reactions and enhancing selectivity. Benefiting from these effects, the 5Co/FeNR achieves 14.6% conversion and 82.7% selectivity for KA oil and mass‐specific reaction rate of 830.7 mmol·g cat −1 ·h −1 , which is approximately 6 times that of FeNR. This study provides valuable insights into the rational design of efficient oxidation catalysts.

Medium‐Sized Intermetallic PtCo Catalysts for Low‐Pt Heavy‐Duty Fuel Cells

ABSTRACT Heavy‐duty vehicles are becoming the primary focus of commercial deployment for proton exchange membrane fuel cells, yet their stringent operating conditions place far greater demands on fuel cell lifetime and efficiency. Meeting these requirements often necessitates elevated Pt loadings, as current cathode catalysts continue to face the challenge of balancing performance and durability under reduced Pt usage. Here, we present a catalyst design and synthesis strategy that overcomes this limitation by high‐temperature pyrolysis of a bimetallic complex to yield a highly ordered L1 0 PtCo intermetallic nanocatalyst (∼80% ordering degree) composed of uniformly dispersed nanoparticles with an average size of ∼6 nm. These structural features enable the synergistic optimization of Gibbs–Thomson energy, Pt─Co bond enthalpy, and compressive strain, imparting the catalyst with outstanding structural and compositional stability while showing high activity. At a low cathode loading of 0.1 mg Pt cm −2 , the resulting catalyst delivers a current density of 1.21 A cm −2 at 0.7 V after 90 000 cycles of accelerated stress testing, corresponding to a Pt utilization of 6.8 kW g Pt −1 , more than two times higher than the U.S. Department of Energy target (2.5 kW g Pt −1 ).

Tuning and Shielding Iridium Active Sites Through Tungsten Electron Buffer for Oxygen Evolution Catalysis

ABSTRACT Efficient and durable oxygen evolution reaction (OER) electrocatalysts under acidic conditions are pivotal for proton‐exchange‐membrane water electrolysis (PEMWE), yet Ir‐based catalysts suffer from activity‐stability trade‐offs caused by facile over‐oxidation and corrosion. Herein, IrO x nanoclusters decorated with W single atoms (W SAs) and supported on N‐doped graphene (defined as W‐IrO x /NG) are synthesized via solvothermal reaction and NH 3 ‐assisted pyrolysis process. In W‐IrO x /NG, W SAs with W–N 3 O 1 configuration are attached onto IrO x nanoclusters through W─O─Ir linkers, forming interfacial covalent connections for efficient charge transfer. W‐IrO x /NG delivers an ultrahigh mass activity of 2998.91 A g Ir −1 at 300 mV overpotential and maintains stable operation for over 250 h at 1 A cm −2 in a PEM electrolyzer with an ultralow Ir loading (0.25 mg Ir cm −2 ). Mechanistic insight analysis uncovers that W atoms serve as electron buffer, donating and storing electrons to regulate the oxidation state of Ir during OER, thereby suppressing irreversible over‐oxidation. Theoretical calculation demonstrates that W SAs with W─N 3 O 1 sites modulate the d ‐band structure of Ir center, lowering the deprotonation barrier of *OH/*OOH intermediates and simultaneously weakening oxo‐species adsorption strength, thus accelerating OER kinetics.

Nickel‐Catalyzed Cross‐Electrophile Coupling of Alkynyl Halides With Allylic Acetates

ABSTRACT We have developed a Ni‐catalyzed cross‐electrophile coupling (XEC) strategy that enables the efficient synthesis of diverse skipped enynes from readily accessible alkynyl halides and allylic acetates. This method exhibits broad substrate scope, accommodating a wide range of aliphatic and aromatic electrophiles, as well as complex natural product‐ and pharmaceutical‐derived motifs, which remains a challenge using the current methods. Mechanistic experiments and DFT studies support a double oxidative addition pathway, wherein Ni 0 preferentially undergoes oxidative addition with the alkynyl halide. To our knowledge, this work represents the first example of a TM‐catalyzed reductive cross‐coupling between two electrophiles for the preparation of skipped enynes. The process proceeds with excellent stereoselectivity and notable regioselectivity, offering a promising platform for future development of asymmetric skipped enynes synthesis.

Two‐Dimensional Metal‐Organic Frameworks as Charge Extraction Media Enabling Binary Organic Solar Cells With 20.70% Efficiency

ABSTRACT Metal‐organic frameworks (MOFs), recognized for their tunable, highly conjugated frameworks and exceptional charge‐transport properties, exhibit significant potential in organic solar cells (OSCs). However, their integration has been hampered by inadequate dispersibility in low‐polarity solvents. Herein, the two‐dimensional MOF materials, Cu‐TCPP and Zn‐TCPP, were synthesized and precisely infiltrated into the upper region of the active layer through an anti‐solvent strategy, which significantly enhanced charge transport through continuous π ‐d conjugation within the MOF layers. Moreover, intermolecular interactions between MOFs and acceptor L8‐BO, including metal‐center coordination and π ‐ π effect enabled by conjugated porphyrin ligands, facilitate superior molecular packing, a double‐fibril structure, and favorable vertical phase separation. Consequently, Zn‐TCPP‐incorporated D18:L8‐BO OSCs achieve an outstanding efficiency of 20.70%, ranking among the highest reported values for binary devices. Meanwhile, the anchoring effect of MOFs significantly enhances the morphological stability of the active layer, endowing the OSCs with over twofold improvement in operational stability. This work not only opens a novel pathway for integrating high‐performance MOF materials into OSCs but also establishes a promising paradigm for constructing efficient charge transport channels and fabricating highly stable, high‐performance organic photovoltaics.

A Safe Approach to <i>meta</i> ‐Fluorinated Pyridines

ABSTRACT Since 1947, the Balz–Schiemann reaction has remained the most popular method for the synthesis of meta ‐fluoropyridines. The method involves dangerous pyridyl diazonium salts and has led to numerous documented explosions. A safe alternative to meta ‐fluoropyridines has now been developed on the basis of a 1,3‐disconnection strategy.

Synergistic Chirality Transmission and Energy Transfer in Clusteroluminescent Cholesteric Cellulose Derivatives for Amplified Circularly Polarized Luminescence

ABSTRACT Cellulose‐based systems provide unique advantages for constructing circularly polarized luminescence (CPL) materials owing to their intrinsic chirality and clusteroluminescence properties. However, harnessing the clusteroluminescence of cellulose for the generation, modulation, and amplification of CPL remains challenging. The present work reports the first example of intrinsic CPL from cellulose derivatives by leveraging the synergistic effects of clusteroluminescence and the supramolecular chirality of the chiral nematic (cholesteric) liquid crystalline phase. Notably, the cholesteric cellulose derivatives can simultaneously transfer their inherent chirality and excitation energy to doped achiral fluorescent dyes, leading to amplified multicolor CPL emissions that extend into the near‐infrared region. By leveraging the selective reflection of cellulose derivative film, integration with achiral fluorescent and afterglow film enables tunable CPL, as well as circularly polarized afterglow. Moreover, multidimensional information encryption display and chiral logic system are successfully developed. This work offers valuable insights into the synergistic role of chirality and clusteroluminescence in biomacromolecules, and establishes a versatile and generalizable platform for constructing clusteroluminescence‐based CPL materials.

Fluorinated Cobalt Sites Enable Solar‐Enhanced Neutral Active Chlorine Electrosynthesis for In Situ Seawater Purification

ABSTRACT The electrocatalytic chlorine evolution reaction (ClER) provides a sustainable approach for converting abundant seawater chloride into highly reactive chlorine species for in situ marine purification. However, the practical implementation remains limited by the need for precious‐metal‐based electrodes to achieve high selectivity, while under neutral conditions, intense competition from the oxygen evolution reaction (OER) and severe anode dissolution compromise both efficiency and stability. Here, we demonstrate a solar‐driven strategy employing surface‐fluorinated cobalt hydroxide nanosheets (Co(OH) x F y ) as an efficient, highly selective, and precious‐metal‐free catalyst for neutral‐pH ClER. This catalyst enables rapid degradation of a broad spectrum of prevalent marine contaminants within seconds, including antibiotics, phenols, and endocrine disruptors. In situ surface‐interrogation scanning electrochemical microscopy (SI‐SECM) and scanning electrochemical cell microscopy (SECCM) combined with theoretical calculations reveal that surface fluorination optimizes the coordination and electronic structure of Co(III) active sites, significantly enhancing intrinsic activity and selectivity, particularly at edge regions. Furthermore, the catalyst uniquely leverages photo‐activation to selectively amplify chlorine generation. Integrated into a membrane‐free photoelectrochemical flow reactor, this approach achieves direct seawater purification with significantly reduced energy demand and carbon emissions, demonstrating compelling promise for scalable, environmentally benign marine water treatment.

Photocatalytic Synthesis of Aromatic Nitriles Using TiO ₂ Nanotubes Decorated With Bismuth Halide Perovskite Nanodots

ABSTRACT The aromatic nitrile synthesis via ammoxidation of methylarenes typically requires harsh reaction conditions (≥ 350°C or ≥ 15 bar O 2 ). Here, TiO 2 nanotubes (NTs) homogeneously decorated with halide perovskite Cs 3 Bi 2 Br 9 (CBB) nanodots (&lt; 2 nm) were established as efficient photocatalysts for the sustainable synthesis of aromatic nitriles. A yield rate up to 353 µmol g −1 h −1 was achieved under mild conditions (100°C–120°C, 1–4 bar, and blue light irradiation) with decent nitrile selectivity (85%–88%). Enhanced photo‐induced charge diffusion and structural stability of CBB nanodots afforded excellent quantum efficiencies (up to 26.7%) and sustained photocatalytic activity in long‐term ammoxidation (45 h). Additionally, 11 methylarenes were successfully converted to the corresponding nitriles over the CBB/TiO 2 NT photocatalyst. Mechanism investigations revealed a synergistic catalytic effect between perovskite nanodots and TiO 2 NTs. CBB nanodots activated benzylic C(sp 3 )–H bonds and promoted the oxidation of aldimine intermediates, while TiO 2 NTs with unique adsorption of alcohol intermediates accelerated their partial oxidation to aldehydes.

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