A ternary composite nanofiber-derived thin membrane electrolyte for solid-state Li metal batteries.

We develop novel membrane electrolytes comprising h-BN-doped poly(ethylene oxide) modified poly(vinylidene fluoride-co-hexafluoropropylene)-nanofibers (h-BN@PEO/PVH) with high ionic conductivity (3.3 × 10-4 S cm-1) and Li+ transference number (0.74), endowing solid LiFePO4//Li batteries with excellent cyclability over 1000 cycles at 60 °C. Our strategy surmounts the ionic conduction-interface stability trade-off and thin dimension-flexibility conflict.

Recent advances on COF-based single-atom and dual-atom sites for oxygen catalysis.

Covalent organic frameworks (COFs) have emerged as promising platforms for the construction of single-atom and dual-atom catalysts (SACs and DACs), owing to their well-defined structures, tunable pore sizes, and abundant active sites. In recent years, the development of COF-based SACs and DACs as highly efficient catalysts has witnessed a remarkable surge. The synergistic interplay between the metal active sites and the COF has established the design and fabrication of COF-based SACs and DACs as a prominent research area in electrocatalysis. These catalytic materials exhibit promising prospects for applications in energy storage and conversion devices. This review summarizes recent advances in the design, synthesis, and applications of COF-based SACs and DACs for oxygen catalysis. The catalytic mechanisms of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are comprehensively explored, providing a comparative analysis to elucidate the correlation between the structure and performance, as well as their functional attributes in battery devices. This review highlights a promising approach for future research, emphasizing the necessity of rational design, breakthroughs, and in-situ characterization to further advance the development of high-performance COF-based SACs and DACs for sustainable energy applications.

Efficient photocatalytic hydrogen production via single-atom Pt anchored hydrogen-bonded organic frameworks.

Constructing single-atom catalysts (SACs) using organic porous framework materials as supports presents a promising approach for developing highly efficient photocatalysts for hydrogen evolution. However, the fabrication of SACs that are both highly stable and active poses a significant challenge, particularly in the precise anchoring of metal single atoms. In this study, we utilized 1,3,6,8-tetra (p-methyl benzoate) pyrene as a ligand to synthesize pyrene-based hydrogen-bonded organic frameworks (denoted as PFC-1) through a self-assembly approach. Subsequently, a liquid-phase photoreduction process was employed to deposit noble metal platinum (Pt) onto PFC-1, resulting in the fabrication of SACs (PFC-1@Pt). Characterization results confirmed that Pt existed in a monatomic state, anchored through PtC and PtO coordination bonds with PFC-1. Serving as electron capture and separation centers, the Pt single atoms effectively suppressed electron-hole recombination, thereby prolonging carrier lifetimes. Consequently, the PFC-1@Pt SAC exhibited efficient hydrogen evolution performance with a rate of 2202.5 µmol g-1 h-1 and maintained photocatalytic activity for over 40 h. Our findings provide a systematic approach for developing efficient and stable SACs based on HOFs, expanding the potential applications of HOF materials in photocatalysis.

Engineering π-Electron Bridge Enables Low-Potential 2D Redox Polymer Anodes for High-Voltage Aqueous All-Organic Batteries.

Here, we propose a novel π-electron bridge engineering strategy to explore a class of dioxin-bridged 2D redox covalent organic polymer (RCOP) as trade-off-breaking anodes for high-voltage aqueous all-organic batteries (AAOBs). By establishing a tunable RCOP platform, we perform theoretical study to scrutinize how bridge units between active sites affect the electrode potential and redox activity for the first time. We discover that compared to common pyrazine bridge, the weakened conjugation and strong electron donor character of the proposed dioxin bridge can induce elevated LUMO level and enriched π-electron populations in active sites, heralding a low electrode potential and enhanced redox activity. Besides, nonaromaticity induced molecular flexibility of dioxin bridge mitigates intermolecular stacking for sufficient active site exposure and charge carrier uptake. To experimentally corroborate this, a new dioxin-bridged RCOP (D-HATN) and its pyrazine-bridged analogue (P-HATN) are synthesized for proof-of-concept demonstration. Hence, D-HATN displays excellent compatibility with Na+/Zn2+/NH4+/H3O+ and obviously lower redox potentials in various electrolytes compared to P-HATN, while affording rapid Grotthuss-type proton conduction and unprecedented durability in acid. Thus,  the D-HATN-involved all-organic proton battery delivers an average output voltage of 0.75 V, which can be further elevated to 1.63 V with alkaline-acidic hybrid electrolyte design, affording markedly-increased specific energy.

Transforming Commercial Polymers into Tough yet Switchable Adhesives by Trident Photoswitch Molecule Doping: Break Adhesion-Switchability Paradox.

Here, a trident molecule doping strategy is introduced to overcome both cohesion-adhesion trade-off and adhesion-switchability conflict, transforming commercial polymers into tough yet photo-switchable adhesives. The strategy involves initial rational design of new trident photoswitch molecules namely TAzo-3 featuring azobenzene and hydroxy-terminated alkyl chains involved rigid-soft tri-branch structure, and subsequent doping into commercial polycaprolactone (PCL) via simple blending. Unique design enables TAzo-3 as a versatile dopant, not only regulating the internal and external supramolecular interaction to balance cohesion and interface adhesion for tough bonding, but also affording marked photothermal effect to facilitate rapid adhesive melting for great photo-switchability. Thus, the optimal TAzo-3-doped PCL (TAzo-3@P) displays markedly-improved bonding performance on diverse substrates compared to linear azobenzene-doped PCL and pure PCL. Impressively, TAzo-3@P on polymethyl methacrylate (PMMA) attains large room-temperature adhesion strength of 6.7 MPa - surpassing most reported adhesives and many commercial adhesives on PMMA, along with easy photo-induced detachment with remarkable switch ratio of 2.09 × 105. Besides, TAzo-3@P can also act as "permanent" adhesives for only adhesion, demonstrating excellent multi-reusability, anti-freezing and waterproof ability. Mechanism studies unveil that the switchable adhesion is closely linked with the dopant molecule structure while rigid-soft coupled trident structures and hydroxy-terminated alkyl chains are key factors.

Designed wrinkles for optical encryption and flexible integrated circuit carrier board.

Patterns on polymers usually have different mechanical properties as those of the substrates, causing deformation or distortion and even detachment of the patterns from the polymer substrates. Herein, we present a wrinkling strategy, which utilizes photolithography to define the area of stress distribution by light-induced physical crosslinking of polymers and controls diffusion of residual solvent to redistribute the stress and then offers the same material for patterns as substrate by thermal polymerization, providing uniform wrinkles without worrying about force relaxation. The strategy allows the recording and hiding of up to eight switchable images in one place that can be read by the naked eye without crosstalk, applying the wrinkled polymer for optical anti-counterfeiting. The wrinkled polyimide film was also utilized to act as a substrate for the creation of fine copper circuit by a full-additive process. It generates flexible integrated circuit (IC) carrier board with copper wire density of 400% higher than that of the state-of-the-art in industry while fulfilling the standards for industrialization.

Rigid-Flexible Coupled Dendritic Molecule Doping: General Approach to Activate Commercial Polymers into Harsh Condition-Tolerant Multi-Reusable Strong Supramolecular Adhesives.

Developing functional adhesives combining strong adhesion, good recyclability and diverse harsh-condition adaptability is a grand challenge. Here, we introduce a general dendritic molecule doping strategy to activate commercial polymers into a new family of supramolecular adhesives integrating high adhesion strength, ultralow temperature, water resistant and multi-reusable properties. Our method involves rational design of a new rigid-flexible coupled dendritic molecule-M4C8OH as a versatile dopant, while simple M4C8OH doping into commercial polymers can modulate internal and external non-covalent interaction to enable H-bonding enhanced interchain cross-linking for tough cohesion along with enhanced interphase interaction. This endows 20 wt % M4C8OH-doped polycaprolactone (PCL) adhesives (PCL-M4C8OH) with improved adhesion strength on various substrates with the maximum increase up to 2.87 times that of PCL. In particular, the adhesion strengths of PCL-M4C8OH on polymethyl methacrylate at 25 °C and -196 °C reach 4.67 and 3.58 MPa-1.9 and 2.3 times those of PCL and superior to diverse commercial adhesives and most reported adhesives. PCL-M4C8OH also displays markedly-improved multi-usability and tolerance against ultralow temperature and diverse wet environments. Mechanism studies reveal the crucial role of M4C8OH molecular structures toward superior adhesion. Our method can be expanded to other polymer matrices, yielding diverse new supramolecular adhesives.

Metal Organic Frameworks as Polysulfide Reaction Modulators for Lithium Sulfur Batteries: Advances and Perspectives.

Currently, lithium sulfur (Li-S) battery with high theoretical energy density has attracted great research interest. However, the diffusion and loss process of intermediate lithium polysulfide during charge-discharge hindered the application of the Li-S battery in modern life. To overcome this issue, metal organic frameworks (MOFs) and their composites have been regarded as effective additions to restrain the LiPS diffusion process for Li-S battery. Benefiting from the unique structure with rich active sites to adsorb LiPS and accelerate the LiPS redox, the Li-S batteries with MOFs modified exhibit superior electrochemical performance. Considering the rapid development of MOFs in Li-S battery, this review summarizes the recent studies of MOFs and their composites as the sulfur host materials, functional interlayer, separator coating layer, and separator/solid electrolyte for Li-S batteries in detail. In addition, the promising design strategies of functional MOF materials are proposed to improve the electrochemical performance of Li-S battery.

Viscoelasticity­Controlled Relaxation in Wrinkling Surface for Multistage Time­Resolved Optical Information Encryption.

As counterfeit techniques continue to evolve, ensuring the security of conventional "static" encryption methods becomes increasingly challenging. Here, the viscoelasticity-controlled relaxation is introduced for the first time in a bilayer wrinkling system by regulating the density of hydrogen bond networks in polymer to construct a "dynamic" encryption material. The wrinkling surface can manipulate light during the dynamic relaxation process, exhibiting three stages with frosted glass, structural color, and mirror reflection. By regulating the viscoelasticity of skin layer through UV irradiation, the wavelength and the relaxation rate of the wrinkles can be controlled. As a result, dynamic wrinkling anti-counterfeiting patterns and time-resolved multistage information encryption are achieved. Crucially, the encryption material is developed as an anti-counterfeiting label for packing boxes in daily applications, allowing the encrypted information to be activated manually and identified by naked eyes, surpassing the existing time-resolved encryption materials in utilization potential. Besides, the dynamic hydrogen bond networks are extended to various dynamic interaction networks, demonstrating the versatility of the dynamic encryption strategy. This work not only provides an additional dimension for dynamic information encryption in daily practical use, but also offers theoretical guidance for the development of advanced optical anti-counterfeiting and smart display materials in the future.

Multipolar Conjugated Polymer Framework Derived Ionic Sieves via Electronic Modulation for Long-Life All-Solid-State Li Batteries.

Here, we build a tunable multipolar conjugated polymer framework platform via pore wall chemistry to probe the role of electronic structure engineering in improving the Li+ conduction by theoretical studies. Guided by theoretical prediction, we develop a new cyano-vinylene-linked multipolar polymer framework namely CNF-COF, which can act as efficient ion sieves to modify solid polymer electrolytes to simultaneously tune Li+ migration and stable Li anodes for long-lifespan all-solid-state (ASS) Li metal batteries at high rate. The dual-decoration of cyano and fluorine groups in CNF-COF favorably regulates electronic structure via multipolar donor-acceptor electronic effects to afford proper energy band structure and abundant electron-rich sites for enhanced oxidative stability, facilitated ion-pair dissociation and suppressed anion movements. Thus, the CNF-COF incorporation into poly (ethylene oxide) (PEO) electrolytes not only renders fast selective Li+ transport but also facilitates the Li dendrite suppression. Specifically, the constructed PEO composite electrolyte with an ultra-low CNF-COF content of only 0.5 wt % is endowed with a wide electrochemical window, a high ionic conductivity of 0.634 mS cm-1 at 60 °C and a large Li+ transference number of 0.81-remarkably outperforming CNF-COF-free counterparts (0.183 mS cm-1 and 0.22). As such, the Li symmetric cell delivers stable Li plating/stripping over 1400 h at 0.1 mA cm-2. Impressively, by coupling with LiFePO4 (LFP) cathodes, the assembled ASS Li battery under 60 °C allows for stable cycling over 2000 cycles at 1 C and over 1000 cycles even at 2 C with a large capacity retention of ~75 %, surpassing most reported ASS Li batteries using PEO-based electrolytes.

Engineering Symmetry-Breaking Centers and d-Orbital Modulation in Triatomic Catalysts for Zinc-Air Batteries.

Unraveling the configuration-activity relationship and synergistic enhancement mechanism (such as real active center, electron spin-state, and d-orbital energy level) for triatomic catalysts, as well as their intrinsically bifunctional oxygen electrocatalysis, is a great challenge. Here we present a triatomic catalyst (TAC) with a trinuclear active structure that displays extraordinary oxygen electrocatalysis for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), greatly outperforming the counterpart of single-atom and diatomic catalysts. The aqueous Zn-air battery (ZAB) equipped with a TAC-based cathode exhibits extraordinary rechargeable stability and ultrarobust cycling performance (1970 h/3940 cycles at 2 mA cm-2, 125 h/250 cycles at 10 mA cm-2 with negligible voltage decay), and the quasi-solid-state ZAB displays outstanding rechargeability and low-temperature adaptability (300 h/1800 cycles at 2 mA cm-2 at -60 °C), outperforming other state-of-the-art ZABs. The experimental and theoretical analyses reveal the symmetry-breaking CoN4 configuration under incorporation of neighboring metal atoms (Fe and Cu), which leads to d-orbital modulation, a low-shift d band center, weakened binding strength to the oxygen intermediates, and decreased energy barrier for bifunctional oxygen electrocatalysis. This rational tricoordination design as well as an in-depth mechanism analysis indicate that hetero-TACs can be promisingly applied in various electrocatalysis applications.

Robust, Ultrafast and Reversible Photoswitching in Bulk Polymers Enabled by Octupolar Molecule Design.

Improving the photoswitching rate and robustness of photochromic molecules in bulk solids is paramount for practical applications but remains an on-going challenge. Here, we introduce an octupolar design paradigm to develop a new family of visible light organic photoswitches, namely multi-branched octupolar Stenhouse Adducts (MOPSAs) featuring a C3-symmetrical A3-(D-core) architecture with a dipolar donor-acceptor (D-A) photochrome in each branch. Our design couples multi-dimensional geometric and electronic effects of MOPSAs to enable robust ultrafast reversible photoswitching in bulk polymers. Specifically, the optimal MOPSA (4 wt %) in commercial polyurethane films accomplishes nearly 100 % discoloration in 6 s under visible light with ∼ 100 % thermal-recovery in 17.4 s at 60 °C, while the acquired kinetics constants are 3∼7 times that of dipolar DASA counterpart and 1∼2 orders of magnitude higher than those of reported DASAs in polymers. Importantly, the MOPSA-doped polymer films sustain 500 discoloration/recovery cycles with slow degradation, superior to the existing DASAs in polymers (≤30 cycles). We discover that multi-dipolar coupling in MOPSA enables enhanced polarization and electron delocalization, promoting the rate-determining thermal cyclization, while the branched and non-planar geometry of MOPSA induces large free volume to facilitate the isomerization. This design can be extended to develop spiropyran or azobenzene-based ultrafast photochromic films. The superior photoswitching performance of MOPSAs together with their high-yield and scalable synthesis and facile film processing inspires us to explore their versatile uses as smart inks or labels for time-temperature indicators, optical logic encryption and multi-levelled data encryption.

Proton-Conductive COF Evenly Embedded Cellulose Aerogels toward Water Harvesting and Spontaneous Sustained Power Generation from Ambient Moisture and Human Respiration.

Herein, we develop a new intelligent moisture-sensitive hybrid aerogel by evenly embedding a proton-conductive covalent organic framework (COF-2SO3H) into a carboxylated cellulose nanofiber network (CNF-C) for water harvesting and spontaneous sustained electricity production from ambient humidity and human respiration. Our strategy first exploits the "suspending agent" role of CNF-C to stably disperse COF materials in water for forming uniform hierarchical hybrid structures. By utilizing the synergy of COF-2SO3H and CNF-C together with their inherent structure merits and surface group effects, the hybrid aerogel displays increased water uptake and ion conductivity. Upon asymmetric moisturization, it can create a self-maintained moisture gradient to engender a concentration difference for mobile Na+ and H+, resulting in efficient charge separation and diffusion. Thus, the hybrid aerogel-based coin-type generator achieves a continuous output voltage of ∼0.55 V for at least 5 h in ambient environments in contrast to that using pure CNF-C and carbon-based generators with transient voltage response. Intriguingly, the wearable generator with an aerogel in a mask is more sensitive to human respiration and achieves repeatable and reliable self-charge for persistent electricity along with an increased output voltage of up to 1.0 V and much faster self-charge (only 3 min), both of which surpass most reported moisture-enabled generators.

Unique Octupolar 2D-Polymer Frameworks as Mixed Conductors and Metal-Free Catalysts for Dual-Promoted Li and S Electrochemistry: Multi-regulation Role of Ethoxylation Chemistry.

Here, we for the first time introduce ethoxylation chemistry to develop a new octupolar cyano-vinylene-linked 2D polymer framework (Cyano-OCF-EO) capable of acting as efficient mixed electron/ion conductors and metal-free sulfur evolution catalysts for dual-promoted Li and S electrochemistry. Our strategy creates a unique interconnected network of strongly-coupled donor 3-(acceptor-core) octupoles in Cyano-OCF-EO, affording enhanced intramolecular charge transfer, substantial active sites and crowded open channels. This enables Cyano-OCF-EO as a new versatile separator modifier, which endows the modified separator with superior catalytic activity for sulfur conversion and rapid Li ion conduction with the high Li+ transference number up to 0.94. Thus, the incorporation of Cyano-OCF-EO can concurrently regulate sulfur redox reactions and Li-ion flux in Li-S cells, attaining boosted bidirectional redox kinetics, inhibited polysulfide shuttle and dendrite-free Li anodes. The Cyano-OCF-EO-involved Li-S cell is endowed with excellent overall electrochemical performance especially large areal capacity of 7.5 mAh cm-2 at high sulfur loading of 8.7 mg cm-2 . Mechanistic studies unveil the dominant multi-promoting effect of the triethoxylation on electron and ion conduction, polysulfide adsorption and catalytic conversion as well as previously-unexplored -CN/C-O dual-site synergistic effect for enhanced polysulfide adsorption and reduced energy barrier toward Li2 S conversion.

Unveiling the Role of Charge Dilution and Anionic Chemistry in Enabling High-Rate p-Type Polymer Cathodes for Dual-Ion Batteries.

Herein, we introduce a p-type redox conjugated covalent organic polymer (p-PNZ) as a universal and high-rate cathode for diverse dual-ion batteries. By constructing an n-type redox counterpart (n-PNZ) with an analogous reticular structure and redox-site composition, we also attain a comparative platform to probe how the redox-site nature and counterion chemistry affect the rate performance of polymer cathodes. It is disclosed that the charge dilution in p-type redox sites and bulky anions engenders their weak interaction and rapid anion diffusion in electrodes, while the trivial interaction of the solvent with anions facilitates anion desolvation and interfacial charge transfer. Thus, p-PNZ possesses rapid surface-controlled redox kinetics with a high anion diffusion coefficient regardless of its inferior porosity and conductivity relative to n-PNZ. Along with a long cycle life of over 50000 cycles, the p-PNZ-engaged Zn-based dual-ion battery with a dilute electrolyte delivers nearly constant capacities of ∼149 mAh g-1 at various rates of ≤10 A g-1─such an unusual rate capability has rarely been observed previously─and retains ∼99 mAh g-1 at 40 A g-1, surpassing the n-PNZ counterpart and most existing p-type organic cathodes. The p-PNZ cathode can also be applied to build high-rate Li-based batteries, signifying its universality, while the "ready-to-charge" character of p-PNZ enables anode-free dual-ion batteries with a high-rate capability and long lifespan.

High-performance fiber-shaped Li-ion battery enabled by a surface-reinforced self-supporting electrode.

Herein, we develop a surface-reinforced self-supporting fiber electrode via the simple-yet-reliable ink-extrusion technology to introduce a thin polymer layer at the electrode surface, which endows the fiber architecture with sufficient rigidity for the subsequent fiber cell assembly. Such fiber LiFePO4//Li4Ti5O12 full cells exhibit high linear capacity output (0.144 mA h cm-1) and energy density (0.267 mW h cm-1).

Photo-Assisted Metal-Air Batteries: Recent Progress, Challenges and Opportunities.

To meet the need of high energy density, long durability, safe and cost-efficient energy conversion and storage devices, metal-air batteries like Li-O2 and Zn-O2 batteries have received enormous attention and were subject to exciting development in the past decade. Photo-assisted strategies that enable the effective combination of photo/electric energy conversion/storage render a new dimension for the conventional metal-air batteries techniques with mere electric energy utilization. Therefore, tremendous research is ongoing in search of more efficient and durable devices with photo-assisted strategies. This review provides an overview of photo-assisted Li-O2 batteries, Zn-O2 batteries, and batteries with various metal/air components. The working mechanism, the basic device architecture and practical performances of various photo-assisted systems are summarized and discussed. Furthermore, certain technical challenges and future opportunities for the photo-assisted metal air batteries are emphasized and discussed in the hope of stimulating further research.

Flexible Solid-State Metal-Air Batteries: The Booming of Portable Energy Supplies.

The rapid development of portable and wearable electronics has given rise to new challenges and provoked research in flexible, lightweight, and affordable energy storage devices. Flexible solid-state metal-air batteries (FSSMABs) are considered promising candidates, owing to their large energy density, mechanical flexibility, and durability. However, the practical applications of FSSMABs require further improvement to meet the demands of long-term stability, high power density, and large operating voltage. This Review presents a detailed discussion of innovative electrocatalysts for the air cathode, followed by a sequential overview of high-performance solid-state electrolytes and metal anodes, and a summary of the current challenges and future perspectives of FSSMABs to promote practical application and large-scale commercialization in the near future.

Engineering Support and Distribution of Palladium and Tin on MXene with Modulation of the d-Band Center for CO-resilient Methanol Oxidation.

The efficiency of direct methanol fuel cell (DMFC) is largely determined by the activity and durability of methanol oxidation reaction (MOR) catalysts. Herein, we present a CO-resilient MOR catalyst of palladium-tin nano-alloy anchored on Se-doped MXene (PdSn0.5 /Se-Ti3 C2 ) via a progressive one-step electrochemical deposition strategy. MOR mass activity resulting from Pd/Se-Ti3 C2 catalyst (1046.2 mA mg-1 ) is over 2-fold larger than that of Pd/Ti3 C2 , suggesting that the introduction of Se atoms on MXene might accelerate the reaction kinetics. PdSn0.5 /Se-Ti3 C2 with Se-doping progress of MXene and the cooperated Pd-Sn sites has a superior MOR mass activity (4762.8 mA mg-1 ), outperforming many other reported Pd-based catalysts. Both experimental results and theoretical calculation reveal that boosted electron interaction of metal crystals with Se-doped MXene and optimized distribution of Pd-Sn sites can modulate the d band center, reduce adsorption energies of CO* at Pd site and enhance OH* generation at Sn site, resulting in highly efficient removal of CO intermediates by reaction with neighboring OH species on adjacent Sn sites.

Cutting COF-like C4 N to Give Colloidal Quantum Dots: Towards Optical Encryption and Bidirectional Sulfur Chemistry via Functional Group and Edge Effects.

Herein, we report the first synthesis of colloidal C4 N quantum dots (QDs) and their functional composites and explore their optical activities and edge-selective polysulfide adsorption-catalysis. As-obtained C4 NQDs are rich in carbonyl groups and edges, allowing good solution processability and facile assembly with other moieties for creating functionalities. While C4 NQDs show normal fluorescence (FL), the QD/poly(vinyl alcohol) (PVA) composites give FL/room-temperature-phosphorescence (RTP) dual-mode emission, enabling the corresponding solution to be used as an encryption ink. The QDs anchored onto carbon nanotubes can be used as a barrier layer to decorate commercial separators, endowing a Li-S cell with excellent cycling stability, high rate capability, and large areal capacity. Computation and experiment studies show that edge sites in C4 N favor polysulfide adsorption and catalysis and the enriched edges and carbonyl groups in QDs synergically promotecatalytic conversion of sulfur species.