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Near-infrared (NIR) emitting phosphors draw much attention because they show great applicability and development prospects in many fields. Herein, a series of inverse spinel-type structured LiGa 5 O 8 phosphors with a high concentration of Cr 3+ activators is reported with a dual emission band covering NIR-I and II regions. Except for strong ionic exchange interactions such as Cr 3+ -Cr 3+ and Cr 3+ clusters, an intervalence charge transfer (IVCT) process between aggregated Cr ion pairs is proposed as the mechanism for the ~1210 nm NIR-II emission. Comprehensive structural and luminescence characterization points to IVCT between two Cr 3+ being induced by structural distortion and further enhanced by irradiation. Construction of the configurational energy level diagram enabled elucidation of this transition within the IVCT process. Therefore, this work provides insight into the emission mechanism within the high Cr 3+ concentration system, revealing a new design strategy for NIR-II emitting phosphors to promote its response., (© 2024 Wiley-VCH GmbH.)

Commercial SSZ-13 zeolite with different n(Si)/n(Al) ratios and from different suppliers were subjected to a post-synthetic treatment in order to create mesopores of up to 15 nm. Furthermore, the materials were modified with copper ions and thoroughly physico-chemically characterized. The modified textural properties varied the nature of copper species, and thus, activity in the selective catalytic reduction of NO x with ammonia (NH 3 -SCR-DeNO x ). Pulsed-field gradient nuclear magnetic resonance (PFG-NMR) studies with hexane as probe liquid revealed improved intracrystalline diffusion for some Cu-containing SSZ-13 materials. The NH 3 -SCR-DeNO x pathways are verified via in situ DR UV-Vis, in situ FT-IR and EPR, temperature-programmed studies as well as SSITKA studies that provide a mechanistic understanding of the reaction. Kinetic modelling results demonstrate the highest NH 3 -SCR-DeNO x reaction rates and up to 20 % lower energy barriers with n(Si)/n(Al) ratio of 6.5 for all modified forms (i. e., (NH 4 )Cu-SSZ-13_6.5 and Cu-SSZ-13_6.5_NaOH/0.1) and cause only negligible parasitic ammonia oxidation. The modelling of the stop-flow experiments further demonstrates that the SCR pathway via the HONO surface intermediate is present but barely contributes to the overall NO conversion compared to the dominant path between adsorbed NH 3 and NO from the gas phase., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

High dark current density (Jd) severely hinders further advancement of near-infrared organic photodetectors (NIR OPDs). Herein, we tackle this grand challenge by regulating molecular crystallinity and aggregation of fully non-fused ring electron acceptors (FNREAs). In contrast to the general trend in terminal halogenation of electron acceptors, TBT-V-F, featuring fluorinated terminals, notably demonstrates crystalline intensification and a higher prevalence predominance of J-aggregate compared to its chlorinated counterpart (TBT-V-Cl). The amalgamation of advantages confers TBT-V-F-based OPDs with more organized active layer morphology and denser molecular packing, resulting in improved charge transport, decreased energetic disorder, and reduced trap density. Consequently, the corresponding self-powered OPDs exhibit a 40-fold decrease in Jd, a remarkable increase in detectivity (D*sh), faster response time, and superior thermal stability compared to TBT-V-Cl-based OPDs. Further interfacial optimization results in an ultra-low Jd of 7.30´10-12 A cm-2 with D*sh over 1013 Jones in 320-920 nm wavelength and a climax of 2.2´1014 Jones at 800 nm for the TBT-V-F-based OPDs, representing one of the best results reported to date. This work paves a compelling material-based strategy to suppress Jd for highly sensitive NIR OPDs, while also illustrates the viability of FNREAs in construction of stable and affordable NIR OPDs for real-world applications., (© 2024 Wiley‐VCH GmbH.)

Chiral luminescent liquid crystal (LC) materials with switchable circularly polarized luminescence (CPL) signals have received extensive attention, in which the use of light stimulation to achieve different CPL states is of great significance. However, there are very few reports on the generation and regulation of CPL signals enabled by blue phase LC (BPLC). Herein, achieving CPL signal inversion based on the phase transition induced by light/temperature stimulation in a BPLC system with a wide room-temperature window is reported. A binaphthalene azo-based chiral photoswitch (S)-switch 3 with high helical twisted power (HTP) and large HTP variation is synthesized, and a BP system with a wide room temperature range is further fabricated by doping (S)-switch 3 and a fluorescence molecule into a bulk LC. By regulating the doping amount of (S)-switch 3, a phase transition from BP to cholesteric (Ch) phase at room temperature is observed upon 365 nm UV light irradiation or during cooling process, and the polarization inversion of CPL signal is correspondingly found due to the different CPL generation mechanisms of BPLC and CLC. This study provides a new strategy for the flexible regulation of CPL signals in a BPLC system., (© 2024 Wiley‐VCH GmbH.)

Metabolic processes in living organisms depend on the synergistic actions of enzymes working in proximity and in concert, catalyzing reactions effectively while regulating the formation of metabolites. This enzyme synergy offers promising therapeutic application for diseases such as alcohol intoxication, cancer, and hyperinflammation. Despite their potential, the clinical translation of enzyme cascades is restricted by challenges including poor enzyme stability, short half-life, and a lack of delivery strategies that maintain enzyme proximity. In this study, multi-enzyme nanocascades synthesized are developed through in situ atom transfer radical polymerization using a zwitterionic monomer. This method markedly enhances enzyme stability and proximity, thereby prolonging their circulation half-life after systemic administration. It is demonstrated that the nanocascades of uricase and catalase effectively reduce uric acid levels without excessive hydrogen peroxide production, providing a potential antidote for hyperuricemia. Moreover, in a murine breast cancer model, the nanocascades of glucose oxidase and catalase inhibited tumor progression and enhanced the therapeutic efficacy of doxorubicin. The prolonged circulation and promoted reaction efficacy of these nanocascades underscore their substantial potential in enzyme replacement therapy and the treatment of various diseases., (© 2024 Wiley‐VCH GmbH.)

Coulombic efficiency of over 99 % is rarely achieved for Li metal anode below -40 °C, hindering the practical application of high-energy-density Li metal batteries under extreme conditions. Herein, limiting factors for Li metal reversibility are investigated utilizing ether-based localized high-concentration electrolytes of different solvent-diluent combinations. We find that along with the desolvation barrier, bulk ion transport properties including ionic conductivity, transference number, and diffusivity are also crucial factors for low-temperature Li deposition behavior. Superior Li metal reversibility was observed within the combination of the solvent with moderately weak solvating power and the diluent with minimal viscosity, highlighting the role of ion transport and the necessity for a trade-off with desolvation. The optimized electrolyte composed of lithium bis(fluorosulfonyl)imide, methyl n-propyl ether, and 1,1,2,2-tetrafluoroethyl methyl ether delivers exceptional Coulombic efficiency of 99.34 % at -40 °C and 98.96 % at -60 °C under a current density of 0.5 mA cm -2 . Furthermore, Li||LiCoO 2 (2.7 mAh cm -2 ) cells demonstrate impressive reversible capacity and cycling stability at these temperatures. This work sheds light on the less-recognized relevance of bulk ion transport to low-temperature performance and provides guidelines for the electrolyte design of Li metal batteries operating in cold environments., (© 2024 Wiley-VCH GmbH.)

Ru-based pyrochlores (e.g., Y 2 Ru 2 O 7-δ ) are promised to replace IrO 2 in polymer electrolyte membrane (PEM) electrolyzers. It is significant to reveal the cliff attenuation on the oxygen evolution reaction (OER) performance of these pyrochlores. In this work, we monitor the structure changes and electrochemical behavior of Y 2 Ru 2 O 7-δ over the OER process, and it is found that the reason of decisive OER inactivation is derived from an insulator transition occurred within Y 2 Ru 2 O 7-δ due to its inner "perfecting" lattice induced by continuous atom rearrangement. Therefore, a stabilization strategy of the Ir-substituted Y 2 Ru 2 O 7-δ is proposed to alleviate this undesirable behavior. The double-exchange interaction between Ru and Ir in [RuO6] and [IrO6] octahedra leads the charge redistribution with simultaneous spin configuration adjustment. The electronic state in newly formed octahedrons centered with Ru 4d 3 (with the state of e g ' ↑↑ a 1g ↑ e g 0 ) and Ir 5d 6 (e g ' ↑↓↑↓ a 1g ↑↓ e g 0 ) relieves the uneven electron distributions in [RuO6] orbital. The attenuated Jahn-Teller effect alleviates atom rearrangement, represented as the mitigation of insulator transition, surface reconstruction, and metal dissolution. As results, the Ir-substituted Y 2 Ru 2 O 7-δ presents the greatly improved OER stability and PEM durability. This study unveils the OER degradation mechanism and stabilization strategy for material design of Ru-based OER catalysts for electrochemical applications., (© 2024 Wiley-VCH GmbH.)

In recent times, diaryliodonium reagents (DAIRs) have witnessed a resurgence as arylating reagents, especially under photoinduced conditions. However, reactions proceeding through electron donor-acceptor (EDA) complex formation with DAIRs are restricted to electron-rich reacting partners serving as donors due to the well-known cage effect. We discovered a practical and high-yielding visible-light-induced EDA platform to generate aryl radicals from the corresponding DAIRs and use them to synthesize key chalcogenides. In this process, an array of DAIRs and dichalcogenides react in the presence of 1,4 diazabicyclo[2.2.2]octane (DABCO) as a cheap and readily available donor, furnishing a variety of di(hetero)aryl and aryl/alkyl chalcogenides in good yields. The method is scalable, features a broad scope with good yields, and operates under open-to-air conditions. The photoinduced chalcogenation technology is suitable for late-stage functionalizations and disulfide bioconjugations and facilitates access to biologically relevant thioesters, dithiocarbamates, sulfoximines, and sulfones. Moreover, the method applies to synthesizing diverse pharmaceuticals, such as vortioxetine, promazine, mequitazine, and dapsone, under amenable conditions., (© 2024 Wiley-VCH GmbH.)

The dynamic structure evolution of heterogeneous catalysts during reaction has gained great attention recently. However, controllably manipulating dynamic process and then feeding back catalyst design to extend the lifetime remains challenging. Herein, we proposed an entropy variation strategy to develop a dynamic CuZn-Co/HEOs catalyst, in which the non-active Co nano-islands play a crucial role in controlling thermal effect via timely capturing and utilizing reaction heat generated on the adjacent active CuZn alloys, thus solving the deactivation problem of Cu-based catalysts. Specifically, heat sensitive Co nano-islands experienced an entropy increasing process of slowly redispersion during the reaction. Under such heat dissipation effect, the CuZn-Co/HEOs catalyst exhibited 95.7 % ethylene selectivity and amazing long-term stability (>530 h) in the typical exothermic acetylene hydrogenation. Aiming at cultivating it as a catalyst with promising industrial potential, we proposed a simple regeneration approach via an entropy decreasing process., (© 2024 Wiley-VCH GmbH.)

Nanoparticles can offer an alternative approach to fabricate phase-change materials. The chemical synthesis of GeTe nanoparticles using organometallic precursors exploits high-boiling solvents and relatively high temperatures (close or even above crystallization temperatures), as reported in the available literature. The aim of this work is the preparation of GeTe nanoparticles by a low-temperature synthetic method exploiting new organometallic precursors and common organic solvents. Indeed, different preparation methods and characterization of GeTe nanoparticles is discussed. The characterization of the prepared nanomaterial was performed on the basis of X-ray diffraction, transmission electron microscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, laser ablation time-of-flight mass spectrometry, Raman scattering spectroscopy, and dynamic light scattering. The results show that the low-temperature synthetic route leads to amorphous GeTe nanoparticles. Exploited organometallic precursor is stabilised by neutral ligand which can be isolated after the reaction and repeatedly used for further reactions. Furthermore, GeTe nanoparticle size can be tuned by the conditions of the synthesis., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Near-infrared light-driven photocatalytic CO 2 reduction (NIR-CO 2 PR) holds tremendous promise for the production of valuable commodity chemicals and fuels. However, designing photocatalysts capable of reducing CO 2 with low energy NIR photons remains challenging. Herein, a novel NIR-driven photocatalyst comprising an anionic Ru complex intercalated between NiAl-layered double hydroxide nanosheets (NiAl-Ru-LDH) is shown to deliver efficient CO 2 photoreduction (0.887 μmol h -1 ) with CO selectivity of 84.81 % under 1200 nm illumination and excellent stability over 50 testing cycles. This remarkable performance results from the intercalated Ru complex lowering the LDH band gap (0.98 eV) via a compression-related charge redistribution phenomenon. Furthermore, transient absorption spectroscopy data verified light-induced electron transfer from the Ru complex towards the LDH sheets, increasing the availability of electrons to drive CO 2 PR. The presence of hydroxyl defects in the LDH sheets promotes the adsorption of CO 2 molecules and lowers the energy barriers for NIR-CO 2 PR to CO. To our knowledge, this is one of the first reports of NIR-CO 2 PR at wavelengths up to 1200 nm in LDH-based photocatalyst systems., (© 2024 Wiley-VCH GmbH.)

C-H bond functionalization involving C,C-palladacycle intermediates provides a unique platform for developing novel reactions. However, the vast majority of studies have been limited to the transformations of C(aryl),C-palladacycles. In sharp contrast, catalytic reactions involving C(alkyl),C(alkyl)-palladacycles have rarely been reported. Herein, we disclose an unprecedented cascade C(sp 3 )-H annulation involving C(alkyl),C(alkyl)-palladacycles. In this protocol, alkene-tethered cycloalkenyl bromides undergo intramolecular Heck/C(sp 3 )-H activation to generate C(alkyl),C(alkyl)-palladacycles, which can be captured by α-bromoacrylic acids to afford tricyclic fused pyridinediones. In addition, this strategy can also be applied to indole-tethered cycloalkenyl bromides to construct pentacyclic fused pyridinediones via suquential Heck dearomatization/C(sp 3 )-H activation/decarboxylative cyclization. Notably, the removal of α-bromoacrylic acids in the reaction of alkene-tethered cycloalkenyl bromides can build an interesting tricyclic skeleton containing a four-membered ring. Preliminary mechanistic experiments indicate that five-membered C(alkyl),C(alkyl)-palladacycles serve as the key intermediates. Meanwhile, density functional theory (DFT) calculations have provided insights into the reaction pathway., (© 2024 Wiley-VCH GmbH.)

Polymetallic oxides with extraordinary electrons/geometry structure ensembles, trimmed electron bands, and way-out coordination environments, built by an isomorphic substitution strategy, may create unique contributing to concertedly catalyze water oxidation, which is of great significance for proton exchange membrane water electrolysis (PEMWE). Herein, well-defined rutile InSnRuO 2 oxides with density-controllable oxygen vacancy (Ov)-free electron polarons are firstly fabricated by in situ isomorphic substitution, using trivalent In species as Ov generators and the adjacent metal ions as electron donors to form orderly and concerted In-Ov-Ru-O-Sn substructures in the tetravalent oxides. For acidic water oxidation, the obtained InSnRuO 2 displays an ultralow overpotential of 183 mV (versus RHE) and a mass activity (MA) of 103.02 A mg Ru -1 , respectively. For a long-term stability test of PEMWE, it can run at a low and unchangeable cell potential (1.56 V) for 200 h at 50 mA cm -2 , far exceeding current IrO 2 ||Pt/C assembly in 0.5 m H 2 SO 4 . Accelerated degradation testing results of PEMWE with pure water as the electrolyte show no significant increase in voltage even when the voltage is gradually increased from 1 to 5 A cm -2 . The remarkably improved performance is associated with the concerted In-Ov-Ru-O-Sn substructures stabilized by the dense Ov-electron polarons, which synergistically activates band structure of oxygen species and adjacent Ru sites and then boosting the oxygen evolution kinetics. More importantly, the self-trapped Ov-electron polaron induces a decrease in the entropy and enthalpy, and efficiently hinder Ru atoms leaching by increasing the lattice atom diffusion energy barrier, achieves long-term stability of the oxide. This work may open a door to design next-generation Ru-based catalysts with polarons to create orderly and asymmetric substructures as active sites for efficient electrocatalysis in PEMWE application., (© 2024 Wiley‐VCH GmbH.)

Chiral liquid crystal supramolecular assembly provides an ideal strategy for constructing excellent circularly polarized luminescence (CPL) materials. However, the chirality transfer in chiral liquid crystals normally occurs at two levels from the configurational chirality to the supramolecular phase chirality. The more precise and more levels of chirality transmission are fascinating but remain challenging. The present work reports the first success of three-level chirality transfer and amplification from configurationally point chirality of small molecules to conformationally helical chirality of helical polymers and finally to supramolecular phase chirality of cholesteric liquid crystals composed of chiral nonfluorescent polymers (P46) and nematic liquid crystals. Noticeably, the helical twisting power of P46 is five-fold larger than its monomer. Full-color and white CPL with maximum luminescence dissymmetry factor up to 1.54 and photoluminescence quantum yield up to 63.8% are realized utilizing helical supramolecular assembly combined with selective reflection mechanism. Also significantly, the electrically stimuli-responsive CPL switching device as well as anti-counterfeiting security, information encryption, and chiral logic gate applications are developed. This study deepens the understanding of chirality transfer and amplification across different hierarchical levels., (© 2024 Wiley‐VCH GmbH.)

Polymer single-chain nanoparticles (SCNPs) have found a wide range of applications spanning catalysts, sensors and nanomedicine. The generation of structured SCNPs from star-shaped polymers with diverse architectures and functionalities affords a new avenue to expand the emerging research area. The large-scale synthesis of structured SCNPs is described by the electrostatics-mediated intramolecular crosslinking of three types of 3-armed star-shaped polymers (T-P4VP, T-PS-b-P4VP, and T-P4VP-b-PS), whose configuration is tunable from spherical to cage-shaped to dumbbell-shaped and star-shaped. The structured SCNPs are amphiphilic and can be used as solid surfactants to stabilize different types of emulsions., (© 2024 Wiley‐VCH GmbH.)

Osteochondral injury is a prevalent condition for which no specific treatment is currently available. This study presents a piezoelectric-conductive scaffold composed of a piezoelectric cartilage-decellularized extracellular matrix (dECM) and piezoelectric-conductive modified gelatin (Gel-PC). The piezoelectricity of the scaffold is achieved through the modification of diphenylalanine (FF) assembly on the pore surface, while the conductive properties of scaffold are achieved by the incorporating poly(3,4-ethylenedioxythiophene). In vitro experiments demonstrate that bone marrow mesenchymal stem cells (BMSCs) undergo biphasic division during differentiation. In vivo studies using a Parma pig model of osteochondral defects demonstrate that the piezoelectric-conductive scaffold exhibits superior reparative efficacy. Notably, the generation of electrical stimulation is linked to joint movement. During joint activity, mechanical forces compress the scaffold, leading to deformation and the subsequent generation of an electric potential difference. The positive charges accumulated on the upper layer of the scaffold attract BMSCs, promoting their migration to the upper layer and chondrogenic differentiation. Meanwhile, the negative charges in the lower layer induce the osteogenic differentiation of BMSCs. Overall, this piezoelectric-conducive scaffold provides a promising platform for the effective repair of osteochondral defects., (© 2024 Wiley‐VCH GmbH.)

Hydrogen boride (HB) nanosheets are recognized as a safe and lightweight hydrogen carrier, yet their hydrogen (H 2 ) generation technique has been limited. In the present study, nitrogen-containing organic heterocycles are mixed with HB nanosheets in acetonitrile solution for visible-light-driven H 2 generation. After exploring various nitrogen-containing heterocycles, the mixture of 1,10-phenanthroline molecules (Phens) and HB nanosheets exhibited significant H 2 generation even under visible light irradiation. The quantum efficiency for H 2 generation of the mixture of HB nanosheets and Phens is 0.6%. Based on spectroscopic and electrochemical analyses and density functional theory (DFT) calculations, it is determined that radical species generated from Phens with electrons and protons donated by HB nanosheets are responsive to visible light for H 2 generation. The HB nanosheets/Phens mixture presented in this study can generate H 2 using renewable energy sources such as sunlight without the need for complex electrochemical systems or heating mechanisms and is expected to serve as a lightweight hydrogen storage/release system., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Single-atom catalysts (SACs), featuring highly uniform active sites, tunable coordination environments, and synergistic effects with support, have emerged as one of the most efficient catalysts for various reactions, particularly for electrochemical CO 2 reduction (ECR). However, the scalability of SACs is restricted due to the limited choice of available support and problems that emerge when preparing SACs by thermal deposition. Here, an in situ reconstruction method for preparing SACs is developed with a variety of atomic sites, including nickel, cadmium, cobalt, and magnesium. Driven by electricity, different oxygen-containing metal precursors, such as MOF-74 and metal oxides, are directly atomized onto nitrogen-doped carbon (NC) supports, yielding SACs with variable metal active sites and coordination structures. The electrochemical force facilitates the in situ generation of bonds between the metal and the supports without the need for additional complex steps. A series of MN x O y (M denotes metal) SACs on NC have been synthesized and utilized for ECR. Among these, NiN x O y SACs using Ni-MOF-74 as a metal precursor exhibit excellent ECR performance. This universal and general SAC synthesis strategy at room temperature is simpler than most reported synthesis methods to date, providing practical guidance for the design of the next generation of high-performance SACs., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Electrochemical nitrate reduction reaction (NO 3 RR) is emerging as a promising strategy for nitrate removal and ammonia (NH 3 ) production using renewable electricity. Although great progresses have been achieved, the crystal phase effect of electrocatalysts on NO 3 RR remains rarely explored. Here, the epitaxial growth of unconventional 2H Cu on hexagonal close-packed (hcp) IrNi template, resulting in the formation of three IrNiCu@Cu nanostructures, is reported. IrNiCu@Cu-20 shows superior catalytic performance, with NH 3 Faradaic efficiency (FE) of 86% at -0.1 (vs reversible hydrogen electrode [RHE]) and NH 3 yield rate of 687.3 mmol g Cu -1 h -1 , far better than common face-centered cubic Cu. In sharp contrast, IrNiCu@Cu-30 and IrNiCu@Cu-50 covered by hcp Cu shell display high selectivity toward nitrite (NO 2 - ), with NO 2 - FE above 60% at 0.1 (vs RHE). Theoretical calculations have demonstrated that the IrNiCu@Cu-20 has the optimal electronic structures for NO 3 RR due to the highest d-band center and strongest reaction trend with the lowest energy barriers. The high electroactivity of IrNiCu@Cu-20 originates from the abundant low coordination of Cu sites on the surface, which guarantees the fast electron transfer to accelerate the intermediate conversions. This work provides a feasible tactic to regulate the product distribution of NO 3 RR by crystal phase engineering of electrocatalysts., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Carbonaceous materials hold great promise for K-ion batteries due to their low cost, adjustable interlayer spacing, and high electronic conductivity. Nevertheless, the narrow interlayer spacing significantly restricts their potassium storage ability. Herein, hierarchical N, S co-doped exfoliated holey graphene (NSEHG) with ultrahigh pyridinic/pyrrolic N (90.6 at.%) and large interlayer spacing (0.423 nm) is prepared through micro-explosion assisted thermal exfoliation of graphene oxide (GO). The underlying mechanism of the micro-explosive exfoliation of GO is revealed. The NSEHG electrode delivers a remarkable reversible capacity (621 mAh g -1 at 0.05 A g -1 ), outstanding rate capability (155 mAh g -1 at 10 A g -1 ), and robust cyclic stability (0.005% decay per cycle after 4400 cycles at 5 A g -1 ), exceeding most of the previously reported graphene anodes in K-ion batteries. In addition, the NSEHG electrode exhibits encouraging performances as anodes for Li-/Na-ion batteries. Furthermore, the assembled activated carbon||NSEHG potassium-ion hybrid capacitor can deliver an impressive energy density of 141 Wh kg -1 and stable cycling performance with 96.1% capacitance retention after 4000 cycles at 1 A g -1 . This work can offer helpful fundamental insights into design and scalable fabrication of high-performance graphene anodes for alkali metal ion batteries., (© 2024 Wiley‐VCH GmbH.)

Perylenediimide-chitosan/γ-poly (glutamic acid) microcapsules sizing (PDI-CS/γ-PGA) core-shell microcapsule is designed and used to establish a novel interphase in carbon fiber/epoxy (CF/EP) composite, and the interfacial property, as well as the damage self-reporting of the composite, is compared with desized carbon fiber (CF-desized)/EP and commercial carbon fiber (CF-COM)/EP composite. The ruptured PDI-CS/γ-PGA microcapsule exhibits strong "turn-on" green fluorescence from the released PDI upon mechanical stimuli. The anchoring of PDI-CS/γ-PGA microcapsule on carbon fiber with PDI-CS/γ-PGA microcapsules sizing (CF@PDI-CS/γ-PGA) surface results in increased chemical activity and roughness, exhibiting a weak green fluorescence signal instead of non-fluorescence on CF-desized and CF-COM surface. The transverse fiber bundle tensile (TFBT) strength of CF@PDI-CS/γ-PGA composite is 80.97% and 31.09% higher than those of CF-desized/EP and CF-COM/EP composite, which is attributed to the mechanical interlocking and chemical bonding interaction between carbon fiber and epoxy matrix by introducing PDI-CS/γ-PGA microcapsule with spherular structure and active groups. After microdroplet testing, the strong "turn-on" green fluorescence signal of the released PDI from the microcapsules is detected in the interfacial debonding regions, realizing the microscopic damage self-reporting of CF@PDI-CS/γ-PGA composite., (© 2024 Wiley‐VCH GmbH.)

Thrombus causes a serious condition characterized by the formation of blood clots in blood vessels or heart, potentially leading to life-threatening emergencies. Photothermal therapy (PTT) serves as a treatment for thrombosis that provides noninvasive thrombus dissolution and fewer bleeding side effects. However, the high temperatures generated by PTT can exacerbate vascular inflammation and promote thrombus recurrence. In this study, a photothermal hydrogen sulfide (H 2 S) nanogenerator (PSA@ADT-OH) is constructed using a perylene-cored photothermal agent (PSA) coassembled with a H 2 S donor ADT-OH. The system PSA@ADT-OH demonstrates outstanding targeting and accumulation efficiency against blood flow shear forces. It also provides sustained H 2 S release at thrombus sites, contributing to antiplatelet aggregation, reactive oxygen species clearance, and vascular healing. This approach opens up new possibilities for advanced thrombus treatment., (© 2024 Wiley‐VCH GmbH.)

Conventional phototherapeutic agents are typically used in either photodynamic therapy (PDT) or photothermal therapy (PTT). However, efficacy is often hindered by hypoxia and elevated levels of heat shock proteins in the tumor microenvironment (TME). To address these limitations, a formylated, near-infrared (NIR)-absorbing and heavy-atom-free Aza-BODIPY dye is presented that exhibits both type-I and type-II PDT actions with a high yield of reactive oxygen species (ROS) and manifests efficient photothermal conversion by precise adjustments to the conjugate structure and electron distribution, leading to a large amount of ROS production even under severe hypoxia. To improve biosafety and water solubility, the dye with an amphiphilic triblock copolymer (Pluronic F-127), yielding BDP-6@F127 nanoparticles (NPs) is coated. Furthermore, inspired by the fact that phototherapy triggers the release of tumor-associated antigens, a strategy that leverages potential immune activation by combining PDT/PTT with immune checkpoint blockade (ICB) therapy to amplify the systemic immune response and achieve the much-desired abscopal effect is developed. In conclusion, this study presents a promising molecular design strategy that integrates multimodal therapeutics for a precise and effective approach to cancer therapy., (© 2024 The Author(s). Advanced Healthcare Materials published by Wiley‐VCH GmbH.)

With the rapid emergence of antibiotic-resistant pathogens, nanomaterial-assisted catalytic sterilization has been well developed to combat pathogenic bacteria by elevating the level of reactive oxygen species including hydroxyl radical (·OH). Although promising, the ultra-short lifetime and limited diffusion distance of ·OH severely limit their practical antibacterial usage. Herein, the rational design and preparation of novel virus-like copper silicate hollow spheres (CSHSs) are reported, as well as their applications as robust artificial bacteriophages for localized bacterial capture and enhanced catalytic sterilization in the treatment of oral infectious diseases. During the whole process of capture and killing, CSHSs can efficiently capture bacteria via shortening the distance between bacteria and CSHSs, produce massive ·OH around bacteria, and further iinducing the admirable effect of bacterial inhibition. By using mucosal infection and periodontitis as typical oral infectious diseases, it is easily found that the bacterial populations around lesions in animals after antibacterial treatment fall sharply, as well as the well-developed nanosystem can decrease the inflammatory reaction and promote the hard or soft tissue repair. Together, the high Fenton-like catalytic activity, strong bacterial affinity, excellent antibacterial activity, and overall safety of the nanoplatform promise its great therapeutic potential for further catalytic bacterial disinfection., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Pore size sieving, Donnan exclusion, and their combined effects seriously affect ion separation of membrane processes. However, traditional polymer-based membranes face some challenges in precisely controlling both charge distribution and pore size on the membrane surface, which hinders the ion separation performance, such as heavy metal ion removal. Herein, the heterocharged covalent organic framework (COF) membrane is reported by assembling two kinds of ionic COF nanosheets with opposite charges and different pore sizes. By manipulating the stacking quantity and sequence of two kinds of nanosheets, the impact of membrane surface charge and pore size on the separation performance of monovalent and multivalent ions is investigated. For the separation of anions, the effect of pore size sieving is dominant, while for the separation of cations, the effect of Donnan exclusion is dominant. The heterocharged TpEBr/TpPa-SO 3 H membrane with a positively charged upper layer and a negatively charged bottom layer exhibits excellent rejection of multivalent anions and cations (Ni 2+ , Cd 2+ , Cr 2+ , CrO 4 2- , SeO 3 2- , etc). The strategy provides not only high-performance COF membranes for ion separation but also an inspiration for the engineering of heterocharged membranes., (© 2024 Wiley‐VCH GmbH.)

Non-precious metal-based nitrogen-doped carbon (M-Nx/C) shows great potential as a substitute for precious metal Pt-based catalysts. However, the conventional pyrolytic methods for forming M-Nx/C active sites are prone to issues such as the lack of synergistic interactions among bimetallic atoms and the potential encasement of active sites, leading to compromised catalytic efficiency and hindered mass transfer. In this work, a highly active FeCo-N-C@U-AC electrocatalyst is developed with a high density of active sites, adequate exposure of catalytic sites, and robust mass transfer capability using the chemical vapor-phase deposition (CVD) technique. The resulting catalyst demonstrates impressive oxygen reduction reaction (ORR) catalytic performance and stability, with half-wave potentials of 0.820 V (0.1 M HClO 4 ) and 0.911 V (0.1 M KOH), respectively. It also exhibits significantly enhanced stability, retaining 93.25% and 98.38% of current after continuous 50 000 s of durability testing, surpassing the retention rates of Pt/C (80.31% in HClO 4 and 84.96% in KOH electrolytes). Notably, when employed as a cathode catalyst in proton exchange membrane fuel cells (PEMFCs) and zinc-air flow batteries (ZAFBs), the FeCo-N-C@U-AC catalyst delivers peak power densities of 859 and 162 mW·cm -2 , respectively, showcasing competitive performance comparable to benchmark Pt/C., (© 2024 Wiley‐VCH GmbH.)

The slow reaction kinetics and severe shuttle effect of lithium polysulfide make Li-S battery electrochemical performance difficult to meet the demands of large electronic devices such as electric vehicles. Based on this, an electrocatalyst constructed by metal phase material (MoS 2 ) and semiconductor phase material (SnS 2 ) with ohmic contact is designed for inhibiting the dissolution of lithium polysulfide with improving the reaction kinetics. According to the density-functional theory calculations, it is found that the heterostructured samples with ohmic contacts can effectively reduce the reaction-free energy of lithium polysulfide to accelerate the sulfur redox reaction, in addition to the excellent electron conduction to reduce the overall activation energy. The metallic sulfide can add more sulfophilic sites to promote the capture of polysulfide. Thanks to the ohmic contact design, the carbon nanotube-MoS 2 -SnS 2 achieved a specific capacity of 1437.2 mAh g -1 at 0.1 C current density and 805.5 mAh g -1 after 500 cycles at 1 C current density and is also tested as a pouch cell, which proves to be valuable for practical applications. This work provides a new idea for designing an advanced and efficient polysulfide catalyst based on ohmic contact., (© 2024 Wiley‐VCH GmbH.)

Determining the optimal method for preparing supramolecular materials remains a profound challenge. This process requires a combination of renewable raw materials to create supramolecular materials with multiple functions and properties, including simple fabrication, sustainability, a dynamic nature, good toughness, and transparency. In this work, a strategy is presented for toughening supramolecular networks based on solid-phase chain extension. This toughening strategy is simple and environmentally friendly. In addition, a series of biobased elastomers are designed and prepared with adjustable performance characteristics. This strategy can significantly improve the transparency, tensile strength, and toughness of the synthesized elastomer. The synthesized biobased elastomers have great ductility, repairability, and recyclability, and they show good adhesion and dielectric properties. A biobased ionic skin is assembled from these biobased elastomers. Assembled ionic skin can sensitively detect external stimuli (such as stretching, bending, compression, or temperature changes) and monitor human movement. The conductive and dielectric layers of the biobased ionic skin are both obtained from renewable raw materials. This research provides novel molecular design approaches and material selection methods for promoting the development of green electronic devices and biobased elastomers., (© 2024 Wiley‐VCH GmbH.)

Photo-responsive materials have garnered significant interest for their ability to react to non-contact stimuli, though achieving self-healing under gentle conditions remains an elusive goal. In this research, an innovative and straightforward approach for synthesizing silicone elastomers is proposed that not only self-heal at room temperature but also possess unique photochromic properties and adjustable mechanical strength, along with being both transparent and reprocessable. Initially, aldehyde-bifunctional dithiophene-ethylene molecules with dialdehyde groups (DTEM) and isocyanurate (IPDI) is introduced into the aminopropyl-terminated polydimethylsiloxane (H 2 N-PDMS-NH 2 ) matrix. Subsequently, palladium is incorporated to enhance coordination within the matrix. These silicone elastomers transition to a blue state under 254 nm UV light and revert to transparency under 580 nm light. Remarkably, they demonstrate excellent thermal stability at temperatures up to 100 °C and show superior fatigue resistance. The optical switching capabilities of the silicone elastomers significantly affect both their mechanical characteristics and self-healing abilities. Notably, the PDMS-DTEM-IPDI-@Pd silicone elastomer, featuring closed-loop photo-switching molecules, exhibits a fracture toughness that is 1.3 times greater and a room temperature self-healing efficiency 1.4 times higher than its open-loop counterparts. This novel photo-responsive silicone elastomer offers promising potential for applications in data writing and erasure, UV protective coatings, and micro-trace development., (© 2024 Wiley‐VCH GmbH.)

As the highly stable and abundant carbon source in nature, the activation and conversion of CO 2 into high-value chemicals is highly desirable yet challenging. The development of Cu(I)/Cu(II)─N tri-site synergistic single-atom catalysts (TS-SACs) with remarkable CO 2 activation and conversion performance is presented, eliminating the need for external additives in cascade reactions. Under mild conditions (40 °C, atmospheric CO 2 ), the catalyst achieves high yields (up to 99%) of valuable 2-oxazolidinones from CO 2 and propargylamine. Notably, the catalyst demonstrates easy recovery, short reaction times, and excellent tolerance toward various functional groups. Supported by operando techniques and density functional theory calculations, it is elucidated that the spatially proximal Cu(I)/Cu(II)─N sites facilitate the coupling of multiple chemical transformations. This surpasses the performance of supported isolated Cu(I) or Cu(II) catalysts and traditional organic base-assisted cascade processes. These Cu(I)/Cu(II)─N tri-site synergistic atom active sites not only enable the co-activation of CO 2 at the Cu(II)─N pair and alkyne at the Cu(I) site but also induce a di-metal locking geometric effect that accelerates the ring closure of cyclic carbamate intermediates. The work overcomes the limitations of single metal sites and paves the way for designing multisite catalysts for CO 2 activation, especially for consecutive activation, tandem, or cascade reactions., (© 2024 Wiley‐VCH GmbH.)

Elucidating the correlation of active sites and catalytic activity in multi-component metal-organic frameworks (MOFs) is key to understanding the mechanism of oxygen evolution reaction (OER), yet it remains nebulous. Herein, a direct pathway combining theoretical prediction with anchoring high-valence metals is proposed on MOFs to reveal the mechanism of the OER reaction. Density functional theory (DFT) predicts that the co-modulation by Mo and Co atoms can enhance the conductance of CoMOF and optimize the adsorption-free energies of the OER intermediates. Guided by the theoretical prediction, the Co-based MOFs grown on Ni foams are doped with high valence Mo, which is used as model catalysts for the quantitative study of the composition-dependent OER performance. With Co/Mo in the ratio of 5:1 for the highest OER activity (impressively overpotential of 324 mV at 100 mA cm -2 and a Tafel slope of 96.07 mV dec -1 ) and excellent stability (maintains for 200 h at 100 mA cm -2 ), the catalysts in this work is superior to commercial benchmarks electrocatalysts (RuO 2 /NF, 420 mV, 199.12 mV dec -1 ). This work sheds light on the tailoring of the active sites of MOFs, which is highly correlated with the activity of the OER., (© 2024 Wiley‐VCH GmbH.)

Long-chain bio-based polyamide has shown promising development prospects due to its excellent properties and green renewable characteristics; however, synthesizing inherently flame-retardant long-chain bio-based polyamide remains a big challenge due to the lack of effective knowledge of the key polymerization process. Herein, intrinsicly flame-retardant long-chain bio-based polyamide 512 (PA512) was synthesized in the presence of a reactive flame retardant with high thermal stability and good water solubility. The reaction conditions and existing problems in each stage of the copolymerization system have been clarified and optimized. By utilizing a two-step pre-polymerization approach, a series of intrinsicly flame-retardant PA512 (FRPA512) with large molecular weight, high phosphorus element content and good mechanical properties were obtained. More importantly, the prepared FRPA512 with 5wt% flame retardant loading exhibited good flame retardancy, showing a limiting oxygen index (LOI) of 28.1% and a vertical burning rating of V-0. This study provides a feasible solution to the common problem in the synthesis of flame-retardant polyamides, while also offering new insights for future modification of polyamide copolymerization., (© 2024 Wiley‐VCH GmbH.)

Machine vision systems that consist of cameras and image-processing components for visual inspection and identification tasks play a critical role in various intelligent applications, including pilotless vehicles and surveillance systems. However, current systems usually possess a limited dynamic range and fixed photoresponsivity, restricting their capability of gaining high-fidelity images when encoding a high-contrast scene. Here, it is shown that a photovoltaic memristor incorporating two antagonistic photovoltaic junctions can autonomously adjust its response to varying light stimuli, enabling the amplification of shadows and inhibition of highlight saturation. Due to the dynamic photodoping effect at the p-n junction with an asymmetrical profile, the photocurrent polarities of the antagonistic memristor can be changed as the light intensity increases. The light-intensity-dependent switchable photovoltaic behaviors match Weber's law where photosensitivity is inversely proportional to the light stimuli. An 11 × 11 memristor array is used to detect a high-contrast scene with light intensities ranging from 1 to 5 × 10 4 µW cm -2 , achieving a similar active contrast adaptation performance compared with the human visual systems (less than 1.2 s at 94 dB). This work paves the way for innovative neuromorphic device designs and may lead to the development of state-of-the-art active visual adaptation photosensors., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Psoriasis is a chronic, immune-mediated disorder characterized by immune regulation disorders and abnormal keratinocyte proliferation. Deucravacitinib (Deu), a selective oral Tyrosine Kinase 2 (TYK2) inhibitor, shows promise in treating psoriasis but may cause systemic side effects and fail to address persistent localized thickened lesions. Herein, a self-locking microneedle (MN) patch with a polyvinyl alcohol (PVA) inner ring loaded with Deu is developed, designed to penetrate the transdermal barriers and dissolve rapidly, downregulating the IL-23/IL-17 pathway and serve as the first line of defense against the spread of skin-originated inflammation. Additionally, Calcipotriol (Cal), a vitamin D derivative, is incorporated into a methacrylated hyaluronic acid (HAMA) backing layer and outer ring that mimics occlusive administration, maintaining localized skin surface retention for prolonged anti-proliferative therapy. The Deu@Cal MN demonstrates satisfactory adhesiveness due to swelling-mediated mechanical interlocking via the outer ring, ensuring targeted drug release at lesion site. Besides its effectiveness in alleviating both skin inflammation and proliferation, it inhibits the differentiation of Th17 cells in the spleen, suggesting potential to reduce systemic inflammation. These findings offer a new therapeutic approach for treating psoriasis and other autoimmune and inflammatory conditions., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Passive daytime radiative cooling (PDRC) presents a promising avenue for efficient thermal management without relying on electrical power. In this study, the potential of integrating Hollow Yttrium-Oxide Spheres (HYSs) within a Polydimethylsiloxane (PDMS) matrix to enhance PDRC is investigated. Through a combination of experimental characterization and computational analysis, the optical properties and radiative cooling performance of PDMS films embedded with HYSs are evaluated. These results demonstrate that HYSs significantly improve both solar reflectivity and long-wave infrared (LWIR) emissivity of the PDMS matrix. Finite-Difference Time-Domain (FDTD) simulations confirm the scattering efficiency of HYSs across various wavelength ranges, highlighting their effectiveness as additives for enhancing the radiative properties of passive cooling materials. Experimental validation reveals enhanced reflectivity and emissivity of PDMS films with embedded HYSs, resulting in superior cooling performance compared to non-HYS counterparts. Overall, this study underscores the potential of HYS-infused PDMS films as a promising solution for passive radiative cooling, with broad applicability in diverse domains requiring efficient thermal management solutions. Additionally, these research insights pave the way for establishing an AI database for passive radiative cooling research, offering new avenues for further exploration and application in this field., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Efficient personal protection has emerged as a crucial approach for reducing pulmonary injury induced by particulate matter (PM). However, current personal protective equipments usually lack essential biosafety concerns and fail to own adsorbing/antioxidant/antibacterial function together, making it a challenge to develop an integrated platform with the above characteristics. Herein, a facile oxygen-free hydrothermal strategy is proposed to synthesize new copper-based metal-organic frameworks, Cu-HHTPs, (HHTP: 2,3,6,7,10,11-hexahydroxytriphenylene), with great adsorbing/antioxidant/antibacterial activity and high biosafety. The Cu-HHTPs can serve as an efficient additive incorporated with various fabrics including cellulose acetate (CA) membrane to achieve novel fabric composites, such as CA@Cu-HHTPs, with ideal scavenging outcome for the main components of PM. Evidenced by the animal experiments, CA@Cu-HHTPs can highly mitigate PM-induced adverse effects via adsorbing PM, scavenging ROS, and killing bacteria, leading to a significant reduction in lung permeability, inflammation and oxidative stress, and pulmonary infection. Last but not least, a two-week exposure of CA@Cu-HHTPs exhibits no obvious damage toward the animals by examining their long-term toxicity. Collectively, this study not only highlights the potential of Cu-HHTPs as attractive additives for the preparation of fabric composites, but also lays out a new concept toward the development of new-generation multifunctional personal protective equipment against PM., (© 2024 Wiley‐VCH GmbH.)

Biological vision is one of the most important parts of the human perception system. However, emulating biological visuals is challenging because it requires complementary photoexcitation and photoinhibition. Here, the study presents a bidirectional photovoltage-driven neuromorphic visual sensor (BPNVS) that is constructed by monolithically integrating two perovskite solar cells (PSCs) with dual-gate ion-gel-gated oxide transistors. PSCs act as photoreceptors, converting external visual stimuli into electrical signals, whereas oxide transistors generate neuromorphic signal outputs that can be adjusted to produce positive and negative photoresponses. This device mimics the human vision system's ability to recognize colored and color-mixed patterns. The device achieves a static color recognition accuracy of 96% by utilizing the reservoir computing system for feature extraction. The BPNVS mem-reservoir chip is also proposed for handing object movement and dynamic color recognition. This work is a significant step forward in neuromorphic sensing and complex pattern recognition., (© 2024 Wiley‐VCH GmbH.)

Polymer dielectrics possess outstanding advantages for high-power energy storage applications such as high breakdown strength (E b ) and efficiency (η), while both of them decrease rapidly at elevated temperatures. Although several strategies have been evaluated to enhance Eb and heat resistance, the discharged energy density (U d ) is still limited by the planar conjugated structure. In this study, a novel approach to manipulate polymer morphology is introduced, thereby influencing dielectric properties. A range of polyurea (PU)-based polymers are predicted from different structural unit combinations by machine learning and synthesized two representative polymers with high dielectric constants (K) and thermal stability. These polymers are combined with PI to form a twisted polymer via hydrogen bonding interactions (HNP). Both experimental results and computational simulations demonstrate the twisted structure disrupts the conjugated structure to widen the bandgap and increase dipole moment through the twisting of polar groups, leading to simultaneous improvements in both K and E b . Consequently, HNP-20% achieves an ultrahigh Ud of 6.42 J cm -3 with an efficiency exceeding 90% at 200 °C. This work opens a new avenue to scalable high Ud all-polymer dielectric for high-temperature applications., (© 2024 Wiley‐VCH GmbH.)

To resist the plastic deformation of polymer particles during hot press molding, high molecular weights, and moduli are required for composites with segregated structures, thus the prepared composites exhibit poor flexibility. Also, larger particle sizes can bring lower percolation thresholds while the ensuing greater deformation destroys the conductive network. Moreover, segregated composites still face preparation complexities. Herein, a facile method for developing flexible composites with large-size segregated structures is proposed. First, silver-coated polydopamine-modified reduced graphene oxide (Ag@PrGO), as conductive fillers, is prepared by electroless plating. Next, polydimethylsiloxane (PDMS)-coated polyolefin elastomer (POE) beads are put into a bag containing the fillers. After a simple shaking, the fillers are adhered to the POE surface as the cohesive property of cured PDMS. Finally, flexible composites with large-size segregated structures are obtained via hot pressing. Benefiting from the 2D structure of the Ag@PrGO and the ability to slip, the conductive networks possess adaptable deformability. The prepared composites exhibit excellent electrical conductivity (203.55 S cm -1 ) at filler volume fractions of 3.4 vol%. The EMI shielding effectiveness can reach 70 dB in the X-band at a thickness of 1.9 mm and remains stable after bending and rubbing damage. This work paves the way for constructing large-size segregated structures., (© 2024 Wiley‐VCH GmbH.)

Traditional methods for the aerobic oxidation of methane to methanol frequently require the use of noble metal catalysts or flammable H2-O2 mixtures. While electrochemical methods enhance safety and may avoid the use of noble metals, these processes suffer from low yields due to limited current density and/or low selectivity. Here, we design an electrothermal process to conduct aerobic oxidation of methane to methanol at room temperature using phosphotungstic acid (PTA) as a redox mediator. When electrochemically reduced, PTA activates methane with O2 to produce methanol selectively. The optimum productivity reaches 29.45 [[EQUATION]] with approximately 20.3% overall electron yield. Under continuous operation, we achieved 19.90 [[EQUATION]] catalytic activity, over 74.3% methanol selectivity, and 10 hours durability. This approach leverages reduced PTA to initiate thermal catalysis in solution phase, addressing slow methane oxidation kinetics and preventing overoxidations on electrode surfaces. The current density towards methanol production increased over 40 times compared with direct electrochemical processes. The in-situ generated hydroxyl radical, from the reaction of reduced PTA and oxygen, plays an important role in the methane conversion. This study demonstrates reduced polyoxotungstate as a viable platform to integrate thermo- and electrochemical methane oxidation at ambient conditions., (© 2024 Wiley‐VCH GmbH.)

Layered double hydroxides (LDHs) have been regarded as excellent catalysts for a variety of photocatalytic applications including the hydrogen production, carbon dioxide reduction, and nitrogen fixation, et al. The elucidation of the photocatalytic mechanism of LDH-based photocatalysts under light irradiation, especially at the ultraviolet (UV) and deep ultraviolet (DUV) region, at the molecular level has remained elusive. In this study, the photo-induced electronic structure of ZnAl-LDH materials were investigated, and a comprehensive understanding of its underlying mechanism, both in the UV and DUV region, was gained using density functional theory (DFT) calculations. The UV and DUV regions exhibit distinct excitation characteristics, revealing the complex interactions between electrons and holes within the system. The DUV region significantly promotes electron transfer, indicating the potential application of LDH materials as a DUV catalysis material. This study elucidates the electron transfer kinetics in LDHs upon UV and DUV irradiation, thereby offering new perspective for the development of photocatalytic materials under different light region., (© 2024 Wiley‐VCH GmbH.)

Developing efficient and earth-abundant alkaline HER electrocatalysts is pivotal for sustainable energy, but co-regulating its intricate multi-step process, encompassing water dissociation, OH- desorption, and hydrogen generation, is still a great challenge. Herein, we tackle these obstacles by fabricating a vertically integrated electrode featuring a nanosheet array with prominent dual-nitride metallic heterostructures characterized by impeccable lattice matching and excellent conductivity, functioning as a multi-purpose catalyst to fine-tune the bonding affinity  with alkaline HER intermediates. Detailed structural characterization and theoretical calculation elucidate that charge redistribution at the heterointerface creates electron-accumulating W-W sites, which reduces the O p-W d and H s-W d interactions vs. single nitride, thereby enhancing OH- transfer and H2 release. As anticipated, the resulting WN-NiN/CFP catalyst demonstrates a gratifying low overpotential of 36.8 mV at 10 mA/cm² for alkaline HER, while concurrently maintaining operational stability for 1300 h at 100 mA/cm² for overall water splitting. This work presents an effective approach to meticulously optimize multiple site-intermediate interactions in alkaline HER, laying the foundation for efficient energy conversion., (© 2024 Wiley‐VCH GmbH.)

The chlorine evolution reaction (CER) is a crucial anode reaction in the chlor-alkali industrial process. Precious metal-based dimensionally stable anodes (DSA) are commonly used as catalysts for CER but are constrained by their high cost and low selectivity. Herein, a Pt dual singe-atom catalyst (DSAC) dispersed on fluorine-doped carbon nanotubes (F-CNTs) is designed for an efficient and robust CER process. The prepared Pt DSAC demonstrates excellent CER activity with a low overpotential of 21 mV to achieve a current density of 10 mA cm -2 and a remarkable mass activity of 3802.6 A g pt -1 at an overpotential around 30 mV, outperforming those of commercial DSA and Pt single-atom catalyst. The excellent CER performance of Pt DSAC is attributed to the high atomic utilization and improved intrinsic activity. Notably, introducing fluorine atoms on CNTs increases the oxidation and chlorination resistance of Pt DSAC, and reduces the demetalization ratio of Pt atoms, resulting in excellent long-term CER stability. Theoretical calculations reveal that several Pt DSAC configurations with optimized first-shell ligands and interatomic distance display lower energy barriers for Cl intermediates generation and weaker ionic Pt-Cl bond interaction, which are favorable for the CER process., (© 2024 Wiley-VCH GmbH.)

Plastic pollution, an increasingly serious global problem, can be addressed through the full lifecycle management of plastics, including plastics recycling as one of the most promising approaches. System design, catalyst development, and product separation are the keys in improving the economics of electrocatalytic plastics recycling. Here, a membrane-free co-production system was devised to produce succinic acid (SA) at both anode and cathode respectively by the co-electrolysis of polybutylene succinate (PBS) waste plastics and biomass-derived maleic acid (MA) for the first time. To this end, Cr 3+ -Ni(OH) 2 electrocatalyst featuring much enhanced 1,4-butanediol (BDO) oxidation reaction (BOR) activity has been synthesized and the role of doped Cr has been revealed as an "electron puller" to accelerate the rate-determining step (RDS) in the Ni 2+ /Ni 3+ cycling. Impressively, an extra-high SA production rate of 3.02 g h -1 and ultra-high apparent Faraday efficiency towards SA (FE apparent =181.5 %) have been obtained. A carbon dioxide-assisted sequential precipitation approach has been developed to produce high-purity SA and byproduct NaHCO 3 solids. Preliminary techno-economic analysis demonstrates that the reported system is economically profitable and promising for future industrial applications., (© 2024 Wiley-VCH GmbH.)

The pursuit of carbon-neutral energy has intensified the interest in green hydrogen production from direct seawater electrolysis, given the scarcity of freshwater resources. While Ni-based catalysts are known for their robust activity in alkaline water oxidation, their catalytic sites are prone to rapid degradation in the chlorine-rich environments of seawater, leading to limited operation time. Herein, we report a Ni(OH) 2 catalyst interfaced with laser-ablated LiFePO 4 (Ni(OH) 2 /L-LFP), derived from spent Li-ion batteries (LIBs), as an effective and stable electrocatalyst for direct seawater oxidation. Our comprehensive analyses reveal that the PO 4 3- species, formed around L-LFP, effectively repels Cl - ions during seawater oxidation, mitigating corrosion. Simultaneously, the interface between in situ generated NiOOH and Fe 3 (PO 4 ) 2 enhances OH - adsorption and electron transfer during the oxygen evolution reaction. This synergistic effect leads to a low overpotential of 237 mV to attain a current density of 10 mA cm -2 and remarkable durability, with only a 3.3 % activity loss after 600 h at 100 mA cm -2 in alkaline seawater. Our findings present a viable strategy for repurposing spent LIBs into high-performance catalysts for sustainable seawater electrolysis, contributing to the advancement of green hydrogen production technologies., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Quercetin, a natural flavonoid with antioxidant, anti-inflammatory, and anticancer properties, faces limitations in clinical application due to its poor solubility and bioavailability. This study presents a novel delivery system utilizing a combination of polyoxyethylene (100) stearyl ether and folic acid to enhance quercetin's effectiveness. We developed folate-conjugated polyoxyethylene (100) stearyl ether-coated liposomes (FA-Brij-LPs) to leverage the unique properties of polyoxyethylene (100) stearyl ether in conjunction with folic acid for targeted delivery. The FA-Brij-LPs were prepared using the thin-film hydration method and characterized for their physicochemical properties, including size, zeta potential, and drug loading capacity. The optimized FA-Brij-LPs exhibited a mean particle size of 147.57 nm, a zeta potential of 32.20 mV, and a drug loading capacity of 9.33%. In vitro studies demonstrated sustained quercetin release and significantly enhanced cellular uptake compared to free quercetin. The Resazurin cell viability assay further revealed superior anticancer efficacy of FA-Brij-LPs. This innovative approach underscores the effectiveness of combining polyoxyethylene (100) stearyl ether with folic acid in enhancing quercetin delivery and its potential applications in cancer therapy., (© 2024 Wiley‐VCH GmbH.)

Zwitterionic membranes demonstrate excellent antifouling property in water purification. The covalent organic frameworks (COFs), due to the ordered channels and abundant organic functional groups, have distinct superiority in constructing zwitterionic surfaces.Here, the zwitterionic COF membrane is prepared with precise framework structures and uniform charge distribution. The negatively charged 4,4'-diaminobiphenyl-2,2'-sisulphonic acid sodium (SA) and positively charged ethidium bromide (EB) fragments are used to react with 1,3,5-triformylphloroglucinol (TP) at the gas-liquid interface to prepare zwitterionic COF membrane. The complementary charged fragments in the inter-layer and inner-layer facilitate the formation of continuous and tight hydration layer on the membrane surface and pore walls to resist the adsorption of pollutants. The zwitterionic COF membrane effectively resists both negatively charged bovine serum albumin and positively charged lysozyme pollutants with flux recovery ratio (FRR) of 97% and 85%, respectively. Furthermore, the regular nano-channels and balanced interactions between water and surface/pore walls of the zwitterionic membrane result in outstanding permeability of up to 146 L m -2 h -1 bar -1 and excellent dye/salt separation selectivity. The water permeation and antifouling mechanism of membranes are elucidated by experimental and molecular dynamics calculation. Zwitterionic COF membranes can find promising applications in preparing high-performance antifouling membranes., (© 2024 Wiley‐VCH GmbH.)

The early diagnosis of liver injury and in situ real-time monitoring of tumor therapy efficacy are important for the enhancement of personalized precision therapy but remain challenging due to the lack of reliable in vivo visualization tools with integrated diagnostic, therapeutic, and efficacy monitoring functions. Herein, a smart second near-infrared window (NIR-II) molecule (BITX-OH) is rationally designed for diagnosis and therapy by vinyl-bridging hydroxyl diphenyl xanthine unit and benzo[cd]indolium skeleton. BITX-OH exhibits high selectivity and sensitivity toward viscosity, exhibiting a significant enhancement (1167-fold) in NIR-II fluorescence at 962 nm. With the assistance of BITX-OH and NIR-II fluorescence imaging, early diagnosis and therapeutic evaluation of non-alcoholic fatty liver (NAFL), as well as in-site real-time monitoring of hepatic fibrosis (HF) in live mice have been successfully achieved, which is at least several hours earlier than the typical clinical test. Notably, BITX-OH displays excellent photothermal conversion efficiency when exposed to an 808 nm laser, which can induce tumor ablation and increase viscosity, thereby enhancing NIR-II fluorescence for the real-time evaluation of photothermal therapy (PTT). This viscosity-based "self-monitoring" strategy provides a convenient and reliable platform for timely obtaining therapeutic feedback to avoid over- or under-treatment, thus enabling personalized precision therapy., (© 2024 Wiley‐VCH GmbH.)

Phase-change materials (PCMs) stand a pivotal advancement in thermal energy storage and management due to their reversible phase transitions to store and release an abundance of heat energy. However, conventional solid-liquid PCMs suffer from fluidity and leakage in their molten state, limiting their applications at advanced levels. Herein, a novel Zn 2+ -crosslinked polyethylene glycol-co-polyphosphazene copolymer (PCEPN-Zn) as a solid-solid PCM through dynamic metal-ligand coordination is first designed and synthesized. The as-synthesized PCEPN-Zn is further integrated with an MXene film to construct a double-layered phase-change composite through layer-by layer adhesion. Owing to the introduction of MXene film with low emissivity, good light absorptivity, and nonflammability, the resultant phase-change composite not only presents a high latent-heat capacity, good thermal stability, high thermal reliability, and excellent shape stability, but also exhibits a superior self-healing ability, good recyclability, high adhesivity, and good flame-retardant performance. It can be easily adhered to on most objects for various application scenarios. With a combination of the excellent functions derived from PCEPN-Zn and MXene film, the developed phase-change composite exhibits broad prospects for versatile applications in the thermal management of CPUs and Li-ion batteries, thermal infrared stealth of high-temperature objects, heat therapy in the clinic, and fire-safety for various scenarios., (© 2024 Wiley‐VCH GmbH.)

The gradual capacity decrease of vanadium redox flow battery (VRFB) over long-term charge-discharge cycling is determined by electrolyte degradation. While it was initially believed that this degradation was solely caused by crossover, recent research suggests that oxidative imbalance induced by hydrogen evolution reaction (HER) also plays a significant role. In this work by using vanadium pentoxides with different impurities content, we prepared three grades of vanadium electrolyte. By measuring electrochemical properties on carbon felt electrode in three-electrode cell and VRFB membrane-electrode assembly we evaluate the influence of impurity content on battery polarization and rate of side reactions which is indicated by the increase of average oxidation state (AOS) during charge-discharge tests and varies from 0.061 to 0.027 day -1 for electrolytes made from 99.1 and 99.9 wt % V 2 O 5 . We found that increase of AOS correlates with the increase of open-circuit voltage of VRFB in the discharged state ranging from 9.6 to 14.9 mV day -1 for highest and lowest electrolyte purity levels, respectively. While AOS increase is significant, it does not solely determine capacity fade. It is demonstrated that the presence of vanadium crossover decreases capacity fade, i. e. levels the contribution of side reactions on capacity drop., (© 2024 Wiley-VCH GmbH.)