bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enhancing the Light‐Induced Actuation of Nickel Oxyhydroxide by Aluminum Doping
Authors: He Nan , Kwan Kin Wa , Ngan Alfonso Hing Wan 
Published: November 2024

AbstractMaterial‐based actuators for developing miniature robotic systems is an emerging field of interest. Transition metal oxides/hydroxides (TMOs) are introduced for light‐induced actuation based on their effective photothermal mechanism of water deintercalation from their turbostratic crystal structures. Previous studies have demonstrated doping different metal ions into TMOs can make the crystals more turbostratic (more disordered), which can be utilized to enhance the light‐induced actuation is hypothesized. This work studies the effectiveness of aluminum (Al) doping in increasing the turbostraticity and hence actuation performance of TMO of nickel oxyhydroxide (NiOOH). Scanning electron microscopy indicates that Al‐doping can be made into the NiOOH directly by soaking into aluminum sulfate solution without forming surface structures or agglomerated precipitates, and transmission electron microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis shows that a more turbostratic phase structure and better hydration capability are acquired. This Al‐doped NiOOH demonstrates enhanced actuation performance by ≈30% compared to the undoped counterpart.
Photothermally‐Engineered Crystallization of GAP‐Se Bulk Chalcogenide Nanocomposites toward the Realization of 3D Gradient Refractive Index Profiles
Authors: Alvarez Roberto , Zachariou Anna , Mingareev Ilya , Loretz Thomas J. , Sharma Rashi , Cook Justin , Blanco Cesar , Richardson Martin C. , Howe Andrew , Lynch Patrick E. , Tagne Gil. B. J. Sop , Wang Kun , Klucinec Jake , Kang Myungkoo , Richardson Kathleen A. 
Published: November 2024

AbstractTailorability of a medium's optical properties, specifically refractive index and dispersion, is key to enabling compact optical designs. Chalcogenide glasses (ChGs) are widely used for infrared (IR) imaging applications, and the development of gradient refractive index (GRIN) optics. This work extends efforts to create and characterize 3D GRIN profiles in bulk multi‐component Ge‐As‐Pb‐Se (GAP‐Se) ChGs through spatially selective conversion of commercial glass to glass ceramic. This work extends prior efforts on bulk and film lab‐scale glass media, to that of a commercially produced material with improved optical homogeneity. Laser‐induced crystallization upon heat treatment results in the formation of high index Pb‐containing crystals that contribute to an increase in the nanocomposite's resulting effective refractive index, neff. The material's induced crystallinity imparted via laser exposure and heat treatment using metrology tools such as refractometry, X‐ray diffraction, FTIR, and TEM are studied. The resulting material response is quantified which is shown to be modulated via laser dose in both lateral and for the first time, axial directions enabling the first demonstration of a true, 3D GRIN profile. By comparing these outcomes to prior radial GRIN structures, the promise of these media as candidate materials for infrared systems.
Photothermal Driven Biomimetic Actuator Based on Asymmetric Microstructure Nb2CTx MXene Film
Authors: Li Nan , Sun Tong , Zhang Chenchu , Fang Guangyou , Wang Yisen 
Published: November 2024

AbstractThe complex preparation process and low sensitivity have hindered the further application of current MXene‐based biomimetic actuators. In this paper, a photothermal biomimetic actuator based on an asymmetric niobium carbide (Nb2CTx) MXene film is prepared using the solution casting method, enabling interactions with various environments. Nb2CTx absorbs incident photons to provide an energy basis for the deformation of the actuator. Polyvinylidene fluoride (PVDF) with excellent film‐forming properties is used to overcome the brittleness of Nb2CTx to improve the flexibility of the film. Additionally, polyethylene (PE) film can increase the coefficient of thermal expansion (CTE) difference between the materials, providing a mechanical basis for the actuator's deformation. The actuator can respond quickly at low optical power density conditions and produce large bending angles (202° in 2.72 s). It also shows excellent performance in applications such as flexible crawling robots (30 mm in 54 s), smart mechanical clamps (lifting objects ten times their own weight), and smart lighting systems (multi‐light source response). These results not only demonstrate the immense potential of PE/PVDF/MXene composites in biomimetic actuation but also provide new inspiration for exploring the application of other types of MXene in this field.
Interphase‐Regulated Room‐Temperature Sodium‐Sulfur Batteries Enabled by a Nonflammable Dual‐Functional Electrolyte
Authors: Liu Yang , Lu Suwan , Weng Shixiao , Xu Jingjing , Tu Haifeng , Wang Zhicheng , Xue Jiangyan , Liu Lingwang , Zhang Fengrui , Sun Guochao , Gao Yiwen , Qian Can , Liu Zheng , Li Hong , Wu Xiaodong 
Published: November 2024

AbstractRoom temperature sodium‐sulfur (RT Na‐S) batteries have attracted significant attention due to their abundant material reserves, low cost, and high theoretical specific capacity. However, the inherent problems of electrodes and complex interfacial reactions hinder the practical applications. In this study, a nonflammable dual‐functional ionic liquid‐based electrolyte is developed, which can form an inorganic‐rich solid electrolyte interphase on the surface of sodium‐metal anode, effectively improving the sodium deposition behavior and inhibiting dendrite growth. Meanwhile, the unique synergistic effect of FSI−/TFSI− and fluoroethylene carbonate (FEC) in nucleophilic substitution with sodium polysulfides are harnessed to modulate a solid‐solid (S8‐Na2S) transition, resulting in the formation of a stable cathode electrolyte interphase (CEI) enhanced with NaF spheres. Consequently, the generation of polysulfides and interfacial side reactions are effectively suppressed by the solid‐solid transition mechanism under CEI protection. Therefore, by optimizing the multi‐component electrolyte, the S@C||Na cell exhibits high capacity, extends lifespan, exceptional rate performance, and enhances safety, showing a specific capacity of 565 mAh g−1 after 500 cycles at 0.2 A g−1. The utilization of this novel electrolyte holds great potential in RT Na‐S batteries, enabling enhanced electrochemical performance and safety.
Hypercrosslinked Metal‐Organic Polyhedra Electrolyte with High Transference Number and Fast Conduction of Li Ions
Authors: Liu Jinjin , Zhang Runhao , Xie Xintai , Wang Juan , Jin Fazheng , Wang Zhifang , Wang Tonghai , Cheng Peng , Lu Jianhao , Zhang Zhenjie 
Published: November 2024

AbstractSolid‐state electrolytes (SSEs) with high Li‐ion transference numbers and fast ionic conductivity are urgently needed for technological innovations in lithium‐metal batteries. To promote the dissociation of ion pairs and overcome the mechanical brittleness and interface defects caused by traditional fillers in polymeric electrolytes, we designed and fabricated a cationic hypercrosslinking metal‐organic polyhedra (HCMOPs) polymer as SSE. Benefiting a three‐component synergistic effect: cationic MOPs, branched polyethyleneimine macromonomer and polyelectrolyte units, the Li‐HCMOP electrolyte possesses a high Li‐ion conductivity, a high Li‐ion transference number and a low activation energy. The LiFePO4/Li battery exhibits high capacity with superior rate performance and cycling stability. Moreover, soluble MOPs serve as high crosslinking nodes to provide excellent mechanical strength for electrolytes and good compatibility with polymers. This work highlights an effective idea of high‐performance MOP‐based solid‐state electrolytes applied in LMBs.
Idealizing Air‐Processed Perovskite Film Competitive by Surface Lattice Etching‐Reconstruction for High‐Efficiency Solar Cells
Authors: Li Hui , Duan Jialong , Zhang Chenlong , Liu Naimin , Ma Linzheng , Duan Xingxing , Dou Jie , Guo Qiyao , He Benlin , Zhao Yuanyuan , Tang Qunwei 
Published: November 2024

AbstractAir‐processed perovskite solar cells are desirable for the large‐scale manufacturing application in the future, yet the presence of moisture and oxygen goes against perovskite crystallization and deteriorates phase stabilization, leading to the formation of substantial defective nano‐impurities, especially on the vulnerable surface. Here, we propose a strategy to simultaneously remove superficial defect layer and solidify the surface by soaking air‐fabricated perovskite film into low‐polar organic esters at elevated temperature to trigger an in situ dynamic surface lattice disassemble and reconstruction process. Molecular dynamics simulations and experimental results indicate that the inorganic CsPbI2Br perovskite is first dissolved and then the Br‐rich phase is recrystallized at solid–liquid interface owing to the balance between weak solubility and high‐temperature induced annealing process, thus hardening the soft surface and releasing the lattice tensile stress, which benefits the minimization of interfacial recombination and improvement of the structural stability. As a result, we prepare a carbon‐based CsPbI2Br device in complete air without precise control on humidity, achieving a champion efficiency of 15.37 % with excellent resistance to harsh attackers. This method offers a promising avenue for overcoming the limit of processing conditions on advancing perovskite‐based optoelectronic devices.
Pseudohalide Anions Driven Structural Modulation in Distorted Tetrahedral Manganese(II) Hybrids Toward Tunable Green‐Red Emissions
Authors: Zhang Shuai , Han Kai , Xia Zhiguo 
Published: November 2024

AbstractMn(II)‐based halides have recently garnered significant interest as emerging luminescence materials for diverse photonic applications. Generally, Mn(II) hybrids with tetrahedral coordination show green emission, however, ones with octahedral coordination give red emission. Herein, we design the synthesis of tetrahedral Mn(II) pseudohalide hybrids, (RPh3P)2MnBrxNCS4−x (R=phenyl, pentyl or methyl; Ph3P=triphenylphosphine; x=1–3), achieved by gradually substituting bromides with pseudohalides (NCS−). Compared to the green‐emitting A2MnBr4 (512 nm), the mixed hybrids exhibit significantly distorted [MnBrxNCS4−X] tetrahedra with high dipole moment, thus leading to the distinct Stokes shift energies and noticeable red shift emission in the range of 549–613 nm. Furthermore, the photoluminescence quantum yield (PLQY) of these hybrids correlates strongly with the pair correlation function of Mn(II) ions, specifically the Mn⋅⋅⋅Mn distance. These findings highlight the critical role of dipole moments in determining the emission properties and expand the luminescent family of Mn(II) pseudohalide hybrids.
Chiral Rotaxane‐Branched Dendrimers as Relays in Artificial Light‐Harvesting Systems with Boosted Circularly Polarized Luminescence
Authors: Xu Xiao‐Qin , Li Wei‐Jian , Zhang Dan‐Yang , Zhu Yu , Xu Wei‐Tao , Wang Yu , Wang Xu‐Qing , Wang Wei , Yang Hai‐Bo 
Published: November 2024

AbstractStarting from AIEgen‐functionalized chiral [2]rotaxane building block, we have successfully synthesized a new class of chiral rotaxane‐branched dendrimers through controllable divergent strategy for the first time, based on which novel chiral artificial light‐harvesting systems (LHSs) were successfully constructed in aqueous phase by sequentially introducing achiral donor and acceptor. More importantly, accompanied by the two‐step Förster resonance energy transfer (FRET) process in the resultant artificial LHSs, the sequentially amplified circularly polarized luminescence (CPL) performances were achieved, highlighting that the chiral rotaxane‐branched dendrimers could serve as excellent relay for both energy transfer and chirality transmission. Impressively, compared with the sole chiral rotaxane‐branched dendrimers, the dissymmetry factors (glum) values of the resultant artificial LHSs were amplified by one order of magnitude up to 0.038, enabling their further applications in information storage and encryption. The proof‐of concept study provides not only a feasible approach for the efficient amplification of CPL performances but also a novel platform for the construction of novel chiral luminescent materials.
Nano‐Springe Enriched Hierarchical Porous MOP/COF Hybrid Aerogel: Efficient Recovery of Gold from Electronic Waste
Authors: Majumder Dipanjan , Fajal Sahel , Shirolkar Mandar M. , Torris Arun , Banyla Yashasvi , Biswas Kishalay , Rasaily Sagarmani , Ghosh Sujit K. 
Published: November 2024

AbstractExtraction of gold from secondary resources such as electronic waste (e‐waste) has become crucial in recent times to compensate for the gradual scarcity of the noble metal in natural mines. However, designing and synthesizing a suitable material for highly efficient gold recovery is still a great challenge. Herein, we have strategically designed rapid fabrication of an ionic crystalline hybrid aerogel by covalent threading of an amino‐functionalized metal‐organic polyhedra with an imine‐linked chemically stable covalent organic framework at ambient condition. The hierarchically porous ultra‐light aerogel featuring imine‐rich backbone, high surface area, and cationic sites have shown fast removal, high uptake capacity (2349 mg/g), and excellent selectivity towards gold sequestration. Besides, the aerogel can extract ultra‐trace gold‐ions from different terrestrial water bodies, aiming towards safe drinking water. This study demonstrates the great potential of the composite materials based on a novel approach to designing a hybrid porous material for efficient gold recovery from complex water matrices.
Benzylic C(sp3)−H Phosphonylation via Dual Photo and Copper Catalysis
Authors: Li Heng‐Hui , Liu Yuwen , Kramer Søren 
Published: November 2024

AbstractAlkyl phosphonates are important motifs in medicinal chemistry, yet their efficient synthesis by direct C(sp3)−H functionalization remains a challenge. Here, we report straightforward access to benzylic phosphonates by direct C(sp3)−H functionalization in a cross‐dehydrogenative‐coupling reaction between non‐specialized alkylarenes and unfunctionalized phosphites. Notably, the C−H substrates are used as the limiting reagents. The scope of benzylic C−H substrates is broad, and the mild reaction conditions allow for good functional group tolerance. Mechanistic studies indicate that the reaction proceeds via a radical pathway rather than the cationic pathway followed for specialized benzylic C−H substrates in previous methods.
Ring‐Opening Metathesis Polymerization of 1,2‐Dihydroazete Derivatives
Authors: Xiong Wei , Gutekunst Will R. 
Published: November 2024

AbstractFischer carbenes have recently found great utility in the construction of degradable metathesis materials, but investigations have been limited to oxygen‐containing enol ether monomers. Here, the ring‐opening metathesis polymerization of 1,2‐dihydroazetes is reported. The polymerization proceeds regioselectively, and the resulting molecular weights are targetable by adjusting the Grubbs initiator loading. Under acidic conditions, the resulting polymers degrade into 3‐aminopropanal derivatives through hydrolysis of the recurring enamide motifs in the polymer backbone. Additionally, the underlying kinetics and thermodynamics of the polymerization were studied through DFT calculations to elucidate the origins of metathesis regioselectivity. This work further expands the suite of monomers available to generate degradable metathesis materials and provides a flexible platform for target applications.
O−O Radical Coupling in Ultrathin Reconstructed Co6.8Se8 Nanosheets for Effective Oxygen Evolution and Zinc‐Air Batteries
Authors: He Chuansheng , Yang Linlin , Dong Chengyuan , Peng Xiaohui , Ibraheem Yousef , Usoltsev Oleg , Simonelli Laura , He Ren , Cabot Andreu , Lu Yizhong 
Published: November 2024

AbstractDesigning ultrathin transition metal electrocatalysts with optimal surface chemistry state is crucial for oxygen evolution reaction (OER). However, the structure‐dependent electrochemical performance and the underlying catalytic mechanisms are still not clearly distinguished. Herein, we synthesize ultrathin Co6.8Se8 nanosheets (NSs) with subnanometer thickness by incorporating catalytically inactive selenium (Se) into ultrathin Co(OH)2, thereby switching the OER reaction pathway from adsorbate evolution mechanism (AEM) to oxide path mechanism (OPM). The prepared ultrathin Co6.8Se8 NSs exhibit an overpotential of 253 mV at 10 mA/cm2, outperforming the mostly reported Co‐based electrocatalysts. Advanced operando synchrotron spectroscopies and X‐ray absorption spectroscopy reveal the ultrathin Co6.8Se8 NSs, whose surface is reconstructed into Se‐doped Co(OH)2 during the OER process, could trigger direct O*−O* radical coupling rather than OOH* intermediates within AEM pathway thus lowering the energy input. Density functional theory calculations confirm that Co6.8Se8 NSs with shorter Co−Co bond length and stable Co−Se bond could optimize the rate‐determining step barrier via OPM pathway. Besides, rechargeable zinc‐air batteries based on Co6.8Se8 NSs exhibit excellent stability for more than 500 h of continuous charge–discharge cycles at 4 mA/cm2. The present study highlights the structural‐dependent switch of OER pathways and provides valuable insights for further development of ultrathin OER catalysts.
An Interstitial Boron Inserted Metastable Hexagonal Rh Nanocrystal for Efficient Hydrogen Oxidation Electrocatalysis
Authors: Han Pengyu , Wu Liqing , Zhang Yu , Yue Jianchao , Jin Yiming , Jia Hongnan , Luo Wei 
Published: November 2024

AbstractConstructing metastable phase structure plays an important role in changing the physicochemical properties and improving the catalytic performance of nanocrystals. Unfortunately, the synthesis of metastable phase metallic nanocrystals is highly challenging, mainly due to the thermodynamically unstable ground‐state. Here, we report a synthesis of unconventional metastable hexagonal rhodium nanocrystal (Bint−Rhhcp/C) via interstitial boron insertion. The insertion of boron atoms into the interstitial sites of cubic Rh lattice not only induces the atomic arrangements from face‐centered cubic (fcc) to hexagonal close‐packed (hcp), but also stabilizes the metastable hexagonal Rh structure. Benefiting from the phase transition and interstitial boron doping, the Bint−Rhhcp/C catalyst exhibits remarkable catalytic performance toward hydrogen oxidation reaction (HOR) under alkaline media, with a mass activity of 1.413 mA μgPGM−1. Experimental measurements including in situ surface‐enhanced infrared absorption spectroscopy (SEIRAS) and density functional theory (DFT) calculations indicate that the strengthened adsorption of hydroxyl species on the electrode surface of Bint−Rhhcp/C is responsible for the reconstruction of interfacial water structure and increased water proportions in the gap region in the electric double layers. As a result, the increased water connectivity and hydrogen bond network facilitate high‐efficiency hydrogen transfer across the interface, thereby boost the alkaline HOR performance.
Total Synthesis of (−)‐Cordycicadin D and 3,4‐trans‐Cordycicadins A and B: Entry to the 3,4‐trans‐Fused Cordycicadin Framework
Authors: Hunt Liam R. , Grant Phillip S. , Shimokura Grace K. , Furkert Daniel P. , Brimble Margaret A. 
Published: November 2024

AbstractCordycicadins A−D are four C20 polyketides, all containing a γ‐lactone fused to a 10‐membered lactone. The proposed biosynthetic pathway for the cordycicadins anticipates the formation of two more natural products which are unknown. We report the total synthesis of (–)‐cordycicadin D and the two anticipated natural products 3,4‐trans‐cordycicadins A and B. The targets were convergently assembled, in a biomimetic fashion, via an efficient ketene trapping‐intramolecular Michael addition sequence that delivered the requisite 3,4‐trans‐fused framework with high diastereoselectivity, enabled by the synthesis of complex dioxenones that serve as in situ ketene precursors. Recognition of the embedded polyketide symmetry enabled the use of a divergent‐convergent synthetic strategy, based on the use of two products from an early‐stage enzymatic resolution. The synthetic routes afforded (–)‐cordycicadin D in 14 steps and 3,4‐trans‐cordycicadins A and B in 13 steps (longest linear sequence). This work confirms the structure of (−)‐cordycicadin D and the observed instability of the anticipated natural product 3,4‐trans‐cordycicadin B during purification may explain why it is yet to be isolated.
Preparation and Properties of Basalt Fiber‐Reinforced Aqueous Polybenzoxazine Composite Aerogels Based on One‐Step Freeze‐Drying Method
Authors: Long Peijiang , Hou Zhaorun , Cheng Jinbo , Li Hui , Zhao Chunxia , Liao Jialin , Wu Yuanpeng , Zhao Haibo , Huang Haoran , Li Yuxing 
Published: November 2024

ABSTRACTPolybenzoxazine (PBa) aerogels have gained much attention as a fire‐retardant material because of their flexible molecular design and excellent mechanical properties. Incorporation of inorganic fibers into PBa aerogels using a simple and effective method seems attractive yet challenging. Herein, we report a unique method for the one‐step preparation of basalt fiber (BF) reinforced PBa composite aerogels by freeze‐drying using carboxymethyl cellulose (CMC) as a dispersion carrier. Aqueous benzoxazine (Ba) monomer was used as the matrix and phosphoric acid was used as the polymerization catalyst, while the uniform dispersion of BF was achieved by blending with CMC. The results indicate that the PBa/CMC/BF composite aerogel reveals a layered microstructure with BF dispersed between the layers. And the composite aerogel achieves a low volume shrinkage (1.11%), and strong mechanical strength (compressive stress of 1.73 MPa at 60% compressive strain). Additionally, TGA analysis reveals that the composite aerogel achieves a higher initial decomposition temperature (> 200°C) and residual mass (> 48 wt%) in a nitrogen atmosphere. Excellent flame retardancy of PBa/CMC/BF composite aerogel is achieved due to the introduction of nonflammable BF: as BF content rises, its peak heat release rate decreases by 92.5%, average heat release by 86.6%, and total smoke release by 76.7%. In combustion tests, the composite aerogel self‐extinguishes within 0.5 s. After hydrophobic modification, the composite aerogel achieves a water contact angle greater than 135°, while PBa/CMC/BF3 exhibits the typical “silver mirror phenomenon” in water. This study presents a straightforward and rapid method for constructing a lightweight, flame retardant, hydrophobic, and high‐strength fiber‐reinforced PBa composite aerogel, with promising applications in the aerospace sector.