bluuebunny/crossref_metadata_2025_split huggingface dataset:
Long‐term Durability of Seawater Electrolysis for Hydrogen: From Catalysts to Systems
Authors: Liu Yu , Wang Yong , Fornasiero Paolo , Tian Ge , Strasser Peter , Yang Xiao‐Yu 
Published: August 2024

AbstractDirect electrochemical seawater splitting is a renewable, scalable, and potentially economic approach for green hydrogen production in environments where ultra‐pure water is not readily available. However, issues related to low durability caused by complex ions in seawater pose great challenges for its industrialization. In this review, a mechanistic analysis of durability issues of electrolytic seawater splitting is discussed. We critically analyze the development of seawater electrolysis and identify the durability challenges at both the anode and cathode. Particular emphasis is given to elucidating rational strategies for designing electrocatalysts/electrodes/interfaces with long lifetimes in realistic seawater including inducing passivating anion layers, preferential OH−adsorption, employing anti‐corrosion materials, fabricating protective layers, immobilizing Cl− on the surface of electrocatalysts, tailoring Cl− adsorption sites, inhibition of OH− binding to Mg2+ and Ca2+, inhibition of Mg and Ca hydroxide precipitation adherence, and co‐electrosynthesis of nano‐sized Mg hydroxides. Synthesis methods of electrocatalysts/electrodes and innovations in electrolyzer are also discussed. Furthermore, the prospects for developing seawater splitting technologies for clean hydrogen generation are summarized. We found that researchers have rethought the role of Cl− ions, as well as more attention to cathodic reaction and electrolyzers, which is conducive to accelerate the commercialization of seawater electrolysis.
Stable Dendrite‐Free Room Temperature Sodium‐Sulfur Batteries Enabled by a Novel Sodium Thiotellurate Interface
Authors: Gao Wanjie , Su Laisuo , Yu Yueheng , Lu Yuhan , Liu Xi , Peng Yi , Xiong Xiaosong , He Jiarui , Chen Yuanfu , Wu Yuping 
Published: August 2024

AbstractThe practical application of room‐temperature sodium‐sulfur (RT Na−S) batteries is severely hindered by inhomogeneous sodium deposition and notorious sodium polysulfides (NaPSs) shuttling. Herein, novel sodium thiotellurate (Na2TeS3) interfaces are constructed both on the cathode and anode for Na−S batteries to simultaneously address the Na dendritic growth and polysulfides shuttling. On the cathode side, a heterostructural sodium sulfide/sodium telluride embedded in a carbon matrix (Na2S/Na2Te@C) is rationally designed through a facile carbothermal reaction, where the Na2TeS3 interface will be in situ chemically obtained. Such an interface provides abundant electron/ion diffusion channels and ensures rich catalytic surfaces toward Na−S redox, which could significantly improve the utilization of active material and alleviate polysulfides shuttling in the cathode. On the anode side, the inevitable formation of soluble polytellurosulfides species will migrate on Na anode surface, finally constructing a compact and smooth solid‐electrolyte Na2TeS3 interphase (SEI) layer. Such electrochemical formed Na2TeS3 interface can significantly enhance ionic transport and stabilize Na deposition, thus realizing dendrite‐free Na‐metal plating/stripping. Benefitting from these advantages, an anode‐free cell fabricated with the Na2S/Na2Te@C cathode exhibits an ultrahigh initial discharge capacity of 634 mAh g−1 at 0.1 C, which could pave a new path to design high‐performance cathodes for anode‐free RT Na−S batteries.
A Dynamically Ion‐Sieved Electrolyte towards Ultralong‐Lifespan Zn‐Ion Batteries
Authors: Ji Yuyao , Hu Qiang , Zhao Jingxin , Han Cuiping , Cheng Hui‐Ming 
Published: August 2024

AbstractThe practical deployment of Zn‐ion batteries faces challenges such as dendrite growth, side reactions and cathode dissolution in traditional electrolytes. Here, we develop a highly conductive and dynamically ion‐sieved electrolyte to simultaneously enhance the Zn metal reversibility and suppress the cathode dissolution. The dynamic ion screen at the electrode/electrolyte interface is achieved by numerous pyrane rings with a radius of 3.69 Å, which can selectively facilitate the plating/stripping and insertion/extraction process of [Zn(H2O)6]2+ and Zn2+ on the anode and cathode surfaces. As a proof of concept, Zn//Zn symmetric cells deliver exceptional cyclic stability for over 6,800 h and ultrahigh cumulative plated capacity of 1.95 Ah cm−2. Zn//Na2Mn3O7 cells exhibit satisfactory cycling performance with capacity retention of 82.7 % after 4,000 cycles, and the assembled pouch cells achieve excellent stability and durability. This work provides valuable insights into the development of electrolytes aimed at enhancing the interface stability of aqueous batteries.
Designing Cooperative Ion Transport Pathway in Ultra‐Thin Solid‐State Electrolytes toward Practical Lithium Metal Batteries
Authors: Feng Guo , Ma Qianyi , Luo Dan , Yang Tingzhou , Nie Yihang , Zheng Zhuoyi , Yang Leixin , Li Shibin , Li Qingying , Jin MingLiang , Wang Xin , Chen Zhongwei 
Published: August 2024

AbstractSolid polymer electrolytes (SPEs) are promising for high‐energy‐density solid‐state Li metal batteries due to their decent flexibility, safety, and interfacial stability. However, their development was seriously hindered by the interfacial instability and limited conductivity, leading to inferior electrochemical performance. Herein, we proposed to design ultra‐thin solid‐state electrolyte with long‐range cooperative ion transport pathway to effectively increase the ionic conductivity and stability. The impregnation of PVDF−HFP inside pores of fluorinated covalent organic framework (CF3−COF) can disrupt its symmetry, rendering rapid ion transportation and inhibited anion immigration. The functional groups of CF3−COF can interact with PVDF−HFP to form fast Li+ transport channels, which enables the uniform and confined Li+ conduction within the electrolyte. The introduction of CF3−COF also enhances the mechanical strength and flexibility of SPEs, as well as ensures homogeneous Li deposition and inhibited dendrite growth. Hence, a remarkably high conductivity of 1.21×10−3 S cm−1 can be achieved. Finally, the ultra‐thin SPEs with an extremely long cycle life exceed 9000 h can be obtained while the NCM523/Li pouch cell demonstrates a high capacity of 760 mAh and 96 % capacity retention after cycling, holding great promises to be utilized for practical solid‐state Li metal batteries.
Selective Activation of Peptide‐Thioester Precursors for Templated Native Chemical Ligations
Authors: Spaltenstein Paul , Giesler Riley J. , Scherer Samuel R. , Erickson Patrick W. , Kay Michael S. 
Published: August 2024

AbstractChemical protein synthesis enables access to proteins that would otherwise be difficult or impossible to obtain with traditional means such as recombinant expression. Chemoselective ligations provide the ability to join peptide segments prepared by solid‐phase peptide synthesis. While native chemical ligation (NCL) is widely used, it is limited by the need for C‐terminal thioesters with suitable reaction kinetics, properly placed native Cys or thiolated derivatives, and peptide segment solubility at low mM concentrations. Moreover, repetitive purifications to isolate ligated products are often yield‐sapping, hampering efficiency and progress. In this work, we demonstrate the use of Controlled Activation of Peptides for Templated NCL (CAPTN). This traceless multi‐segment templated NCL approach permits the one‐pot synthesis of proteins by harnessing selective thioester activation and orthogonal conjugation chemistries to favor formation of the full‐length ligated product while minimizing side reactions. Importantly, CAPTN provides kinetic enhancements allowing ligations at sterically hindered junctions and low peptide concentrations. Additionally, this one‐pot approach removes the need for intermediate purification. We report the synthesis of two E. coli ribosomal subunits S16 and S17 enabled by the chemical tools described herein. We anticipate that CAPTN will expedite the synthesis of valuable proteins and expand on templated approaches for chemical protein synthesis.
Aza‐Diarylethenes Undergoing Both Photochemically and Thermally Reversible Electrocyclic Reactions
Authors: Hamatani Shota , Kitagawa Daichi , Kobatake Seiya 
Published: August 2024

AbstractExploring novel molecular photoswitches plays a crucial role in the field of photo‐functional materials chemistry. In this study, we synthesized aza‐diarylethenes with benzothiophene‐S,S‐dioxide as a part of the hexatriene structure and investigated their photochromic properties. Unlike previously reported aza‐diarylethenes, which exhibit fast thermally reversible photochromism, the compounds synthesized here exhibited pseudo‐photochemically reversible photochromism. Due to their thermal stability, we successfully isolated the colored isomer. X‐ray crystallographic analysis revealed for the first time that the colored isomer adopts a closed‐ring structure with a bond between carbon and nitrogen atoms. Remarkably, these aza‐diarylethenes exhibited not only photochemical ring‐closing and ring‐opening reactions but also thermal ring‐closing and ring‐opening reactions, driven by a thermal equilibrium between the open‐ and closed‐ring isomers. This behavior, unprecedented for common diarylethenes, was elucidated through kinetic analysis, revealing an energy‐level diagram for the thermal equilibrium between these isomers. Furthermore, 1H NMR spectroscopy revealed that both photochemically and thermally generated closed‐ring isomers adopt the same molecular structure, which was well explained based on the reaction mechanism of photochemical and thermal ring‐closing reactions. These findings not only advance the field of aza‐diarylethenes but also inspire future research in the development of new photoswitches.
Bidirectional Molecular Motors by Controlling Threading and Dethreading Pathways of a Linked Rotaxane
Authors: Miyagishi Hiromichi V. , Masai Hiroshi , Terao Jun 
Published: August 2024

AbstractArtificial molecular motors have been presented as models for biological molecular motors. In contrast to the conventional artificial molecular motors that rely on covalent bond rotation, molecular motors with mechanically interlocked molecules (MIMs) have attracted considerable attention owing to their ability to generate significant rotational motion by dynamically shuttling macrocyclic components. The topology of MIM‐type rotational molecular motors is currently limited to catenane structures, which require intricate synthetic procedures that typically produce a low synthetic yield. In this study, we develop a novel class of MIM‐type molecular motors with a rotaxane‐type topology. The switching of the threading/dethreading pathways of the linked rotaxane by protecting/deprotecting the bulky stopper group and changing the solvent polarity enables a net unidirectional rotation of the molecular motor. The threading/dethreading reaction rates were quantitatively evaluated through detailed spectroscopic investigations. Repeated net unidirectional rotation and switching of the direction of rotation were also achieved. Our findings demonstrate that linked rotaxanes can serve as MIM‐type molecular motors with reversible rotational direction controlled by threading/dethreading reactions. These motors hold potential as components of molecular machinery.
High‐Stable All‐Iron Redox Flow Battery with Innovative Anolyte based on Steric Hindrance Regulation
Authors: Yang Jiahui , Wei Wei , Zhou Chengxi , Yan Hui , Che Hangxin , Hao Leiduan , Tan Xinyi , Robertson Alex W. , Wu Tai‐Sing , Soo Yun‐Liang , Tang Ao , Sun Zhenyu 
Published: August 2024

AbstractAll‐soluble all‐iron redox flow batteries (AIRFBs) are an innovative energy storage technology that offer significant financial benefits. Stable and affordable redox‐active materials are essential for the commercialization of AIRFBs, yet the battery stability must be significantly improved to achieve practical value. Herein, ferrous complexes combined with the triisopropanolamine (TIPA) ligand are identified as promising anolytes to extend battery life by reducing cross‐contamination due to a pronounced steric hindrance effect. The coordination structure and failure mechanism of our Fe‐TIPA complexes were determined by molecular dynamics simulation and spectroscopic experiments. By coupling with [Fe(CN)6]4−/3−, Fe‐TIPA/Fe‐CN AIRFBs retained excellent stability exceeding 1831 cycles at 80 mA ⋅ cm−2, yielding an energy efficiency of ~80 % and maintaining a steady discharge capacity. Moreover, the all‐soluble electrolyte was tested in an industrial‐scale Fe‐TIPA/Fe‐CN AIRFB prototype energy storage system, where an energy efficiency of 81.3 % was attained. Given the abundance of iron resources, we model the TIPA AIRFB electrolyte cost to be as low as 32.37 $/kWh, which is significantly cheaper than the current commercial level. This work demonstrates that steric hindrance is an effective measure to extended battery life, facilitating the commercial development of affordable flow batteries.
Robust Sandwich‐Structured Thermally Activated Delayed Fluorescence Molecules Utilizing 11,12‐Dihydroindolo[2,3‐a]carbazole as Bridge
Authors: Lan Xia , Zeng Jiajie , Chen Jinke , Yang Tao , Dong Xiaobin , Tang Ben Zhong , Zhao Zujin 
Published: August 2024

AbstractConstructing folded molecular structures is emerging as a promising strategy to develop efficient thermally activated delayed fluorescence (TADF) materials. Most folded TADF materials have V‐shaped configurations formed by donors and acceptors linked on carbazole or fluorene bridges. In this work, a facile molecular design strategy is proposed for exploring sandwich‐structured molecules, and a series of novel and robust TADF materials with regular U‐shaped sandwich conformations are constructed by using 11,12‐dihydroindolo[2,3‐a]carbazole as bridge, xanthone as acceptor, and dibenzothiophene, dibenzofuran, 9‐phenylcarbazole and indolo[3,2,1‐JK]carbazole as donors. They hold outstanding thermal stability with ultrahigh decomposition temperatures (556–563 °C), and exhibit fast delayed fluorescence and excellent photoluminescence quantum efficiencies (86 %–97 %). The regular and close stacking of acceptor and donors results in rigidified molecular structures with efficient through‐space interaction, which are conducive to suppressing intramolecular motion and reducing reorganized excited‐state energy. The organic light‐emitting diodes (OLEDs) using them as emitters exhibit excellent electroluminescence performances, with maximum external quantum efficiencies of up to 30.6 %, which is a leading value for the OLEDs based on folded TADF emitters. These results demonstrate the proposed strategy of employing 11,12‐dihydroindolo[2,3‐a]carbazole as bridge for planar donors and acceptors to construct efficient folded TADF materials is applicable.
Asymmetric Coupled Binuclear‐Site Catalysts for Low‐Temperature Selective Acetylene Semi‐Hydrogenation
Authors: Lu Fei , Wang Jingnan , Chai Shanshan , Wang Yan , Yao Yongbin , Wang Xi 
Published: August 2024

AbstractHeterogeneous metal catalysts with bifunctional active sites are widely used in chemical industries. Although their improvement process is typically based on trial‐and‐error, it is hindered by the lack of model catalysts. Herein, we report an effective vacancy‐pair capturing strategy to fabricate 12 heterogeneous binuclear‐site catalysts (HBSCs) comprising combinations of transition metals on titania. During the synthesis of these HBSCs, proton‐passivation treatment and step‐by‐step electrostatic anchorage enabled the suppression of single‐atom formation and the successive capture of two target metal cations on the titanium–oxygen vacancy‐pair site. Additionally, during acetylene hydrogenation at 20 °C, the HBSCs (e.g., Pt1Pd1−TiO2) consistently generated more than two times the ethylene produced by their single‐atom counterparts (e.g., Pd1−TiO2). Furthermore, the Pt1Pd1 binuclear sites in Pt1Pd1−TiO2 were demonstrated to catalyze C2H2 hydrogenation via a bifunctional active‐site mechanism: initially C2H2 chemisorb on the Pt1 site, then H2 dissociates and migrates from Pd1 to Pt1, and finally hydrogenation occurs at the Pt1−Pd1 interface.
Non‐Fluorinated Cyclic Ether‐Based Electrolyte with Quasi‐Conjugate Effect for High‐Performance Lithium Metal Batteries
Authors: Zhu Xiao , Chen Jiawei , Liu Gaopan , Mo Yanbing , Xie Yihua , Zhou Kang , Wang Yonggang , Dong Xiaoli 
Published: August 2024

AbstractFluorinated ether‐based electrolytes are commonly employed in lithium metal batteries (LMBs) to attenuate the coordination ability of ether solvents with Li+ and induce inorganic‐rich interphase, whereas fluorination inevitably introduces exorbitant production expenses and environmental anxieties. Herein, a non‐fluorinated molecular design strategy has been conceptualized by incorporating methoxy as an electron‐donating group to generate a quasi‐conjugate effect for tuning the affinity of Li+‐solvent, thereby enabling the cyclic ether solvent 2‐methoxy‐1,3‐dioxolane with weak solvation ability and exceptional Li metal‐compatibility. Accordingly, the optimized electrolyte exhibits anion‐dominant solvation structure for inorganic‐rich interphase and fulfills an impressive Li plating/stripping Coulombic efficiency of 99.6 %. As‐fabricated Li||LiFePO4 full cells with limited Li (N/P=2.5) showcase a high capacity retention of 83 % after 150 cycles, indicating excellent cycling stability. Moreover, the full LMBs demonstrate exceptional tolerance towards a wide temperature range from −20 °C to 60 °C, displaying a remarkable capacity retention of 90 % after 110 cycles at −20 °C. Such a molecular design strategy offers a promising avenue for electrolyte engineering beyond fluorination in order to cultivate high‐performance LMBs.
Constructing Targeted Strong Nb4d−O2p−Li2s Configurations to Obtain Excellent Energy Density and Long Life for Li‐Rich Cathodes
Authors: Hu Kanghui , Tang Huoqiang , Zheng Baoping , Yu Lei , Xiong Feng , Li Haoyu , Qiu Lang , Wan Fang , Song Yang , Zhong Benhe , Wu Zhenguo , Guo Xiaodong 
Published: August 2024

AbstractThe Li‐rich Mn‐based cathode materials (LMRs) deliver excellent energy density and exhibit low cost, which are considered as the most promising cathode materials for the next generation lithium‐ion batteries. However, the irreversible redox reaction of the oxygen atoms directly leads to release oxygen and intensifies phase transformation. Besides, the local stress and strain will be generated due to the unit‐cell volume difference between R‐3m and C2/m phases, which continuously aggravates the collapse of secondary particles. Herein, the strong Nb4d−O2p−Li2s configurations at the Li1 sites of the TM‐layer in the C2/m phase and secondary particles with the radial arrangement of refined primary particles are designed to inhibit oxygen release and relieve lattice stress by Nb2O5 treatment. Meanwhile, the preferential growth of the active {010} planes is presented to obtain an excellent transmission rate of Li+. As a result, the designed LMR delivers remarkable electrochemical properties with high discharge capacity and initial coulomb efficiency of 276 mAh g−1 and 85 % at 0.1 C, outstanding cycling retention rate of 81 % after 300 cycles. This novel crystal structure combining oxygen coordination regulation and micro‐nano scale design provides inspiration for the design of high‐performance LMRs.
Spiral‐Concave Prussian Blue Crystals with Rich Steps: Growth Mechanism and Coordination Regulation
Authors: Zhang Guangxun , Li Yong , Du Guangyu , Lu Jingqi , Wang Qiujing , Wu Ke , Zhang Songtao , Chen Han‐Yi , Zhang Yizhou , Xue Huai‐Guo , Shakouri Mohsen , Liu Zheng , Pang Huan 
Published: August 2024

AbstractInvestigating the formation and transformation mechanisms of spiral‐concave crystals holds significant potential for advancing innovative material design and comprehension. We examined the kinetics‐controlled nucleation and growth mechanisms of Prussian Blue crystals with spiral concave structures, and constructed a detailed crystal growth phase diagram. The spiral‐concave hexacyanoferrate (SC‐HCF) crystals, characterized by high‐density surface steps and a low stress‐strain architecture, exhibit enhanced activity due to their facile interaction with reactants. Notably, the coordination environment of SC‐HCF can be precisely modulated by the introduction of diverse metals. Utilizing X‐ray absorption fine structure spectroscopy and in situ ultraviolet‐visible spectroscopy, we elucidated the formation mechanism of SC‐HCF to Co‐HCF facilitated by oriented adsorption‐ion exchange (OA‐IE) process. Both experimental data, and density functional theory confirm that Co‐HCF possesses an optimized energy band structure, capable of adjusting the local electronic environment and enhancing the performance of the oxygen evolution reaction. This work not only elucidates the formation mechanism and coordination regulation for rich steps HCF, but also offers a novel perspective for constructing nanocrystals with intricate spiral‐concave structures.
A simple subtropical high‐pressure system index over the South Atlantic
Authors: Quagraine Kwesi A. , Hewitson Bruce , Nkrumah Francis , Quagraine Kwesi T. , Egbebiyi Temitope S. 
Published: August 2024

AbstractThis research introduces a novel index for the South Atlantic High Pressure (SAHP) system to enhance understanding of regional climate variability and change. Subtropical highs significantly influence regional climates, yet comprehensive indices to measure their behaviours are lacking. Utilizing ERA5 reanalysis data from 1940 to 2023, the proposed index estimates a weighted centroid of the area surrounding the maximum sea level pressure within a 3 hPa range. This method ensures robustness and flexibility in contiguous area estimation specific to subtropical high events. Results showed the index effectively reflects the position and intensity of the SAHP. The study reveals that latitudinal variability of the SAHP has a strong unimodal structure, whereas longitudinal variability exhibits a bimodal structure. Seasonal patterns of the index show noticeable changes, with winter (JJA) and spring (SON) months having relatively high index values compared to summer (DJF) and autumn (MAM) months, underscoring the intra‐annual variability of the SAHP index. During ENSO events, the mean centroid position of the SAHP shifts significantly, moving westwards and polewards during El Niño and showing greater stability during La Niña. The index, with minimal computation requirements and flexibility, can be applied across diverse datasets, aiding in the assessment of future subtropical high changes.