bluuebunny/crossref_metadata_2025_split huggingface dataset:
Complementary Functions of Vanadium in Boosting Electrocatalytic Activity of CuCoNiFeMn High‐Entropy Alloy for Water Splitting
Authors: Sivanantham Arumugam , Lee Hansung , Hwang Sung Won , Lee Han Uk , Cho Sung Beom , Ahn Byungmin , Cho In Sun 
Published: May 2023

AbstractHigh entropy alloys (HEAs) composed of multi‐metal elements in a single crystal structure are attractive for electrocatalysis. However, identifying the complementary functions of each element in HEAs is a prerequisite. Thus, VxCuCoNiFeMn (x = 0, 0.5, and 1.0) HEAs are investigated to identify the active role of vanadium in improving the electrocatalytic activity for the hydrogen evolution reaction (HER). Structural studies show the successful incorporation of V in the HEA. V1.0CuCoNiFeMn (V1.0‐HEA) shows an overpotential of 250 mV versus the reversible hydrogen electrode (at −50 mA cm−2, 1 m KOH), which is ≈170 mV lower than that of control‐HEA (422 mV). Improves electrical conductivity and the electrochemical surface area of the V1.0‐HEA accelerated HER activity. Furthermore, density functional theory calculations reveal reduced water dissociation and hydrogen adsorption energies of V1.0‐HEA, resulting in the boosted HER kinetics. The effect of V incorporation on the barrier height and active sites at the surface of V1.0‐HEA is schematically explained. This study can be facilitated for the development of highly active HEAs for large‐scale electrochemical water splitting.
Dendrite‐Free Lithium Metal Battery Enabled by Dendritic Mesoporous Silica Coated Separator
Authors: Ren Wenxuan , Zhu Kerun , Zhang Wei , Liang Haichen , Xu Li , Wang Lipeng , Yang Chaochao , Yang Yi , Zhang Pengfei , Wang Fei , Wang Yonggang , Li Wei 
Published: May 2023

AbstractConcentration polarization‐induced lithium dendrites seriously impede the practical application of high‐energy‐density lithium metal batteries. Porous materials that aim to inhibit lithium dendrites are extensively explored. However, their effects are still limited by the intrinsic features of the pores, especially channel geometry and surface properties. Herein, a separator modification strategy of blocking “dendritic deposition” via “dendritic channels” is proposed. A porous shield‐like film is formed on the polypropylene separator through the close packing of ultra‐small (≈100 nm) silica nanospheres with unique dendritic mesopores (DMS). Besides the hierarchical pores homogenizing the ion flux, the DMS film also provides abundant Si(OH)x groups, preferentially adsorbing the TFSI− in the electrolyte and accelerating the transport of Li+. Most notably, the dendritic mesochannels with high complexity can diversify the growth directions of lithium and contribute to a more substantial homogenizing process of Li+. Consequently, a dendrite‐free deposition with 1000 stable cycles in Li|Li symmetric cells even at 10 mA cm−2 is achieved. This study provides a scalable approach for the fabrication of mesoporous separators and offers a fresh perspective on the future design of advanced separators utilized for dendrite suppression.
Orchestrated Strategies for Developing Fluorophores for NIR‐II Imaging
Authors: Feng Xin , Wei Long , Liu Yanlin , Chen Xiaoyuan , Tian Rui 
Published: May 2023

AbstractFluorescence imaging (FLI), a non‐invasive, real‐time, and highly sensitive imaging modality, allows for investigating the molecular/cellular level activities to understand physiological functions and diseases. The emergence of the second near‐infrared window (NIR‐II, 1000–1700 nm) has endowed fluorescence imaging with deeper tissue penetration and unprecedented clarity. Among the various NIR‐II imaging fluorophores, the organic fluorescent probes have occupied a pivotal position in bioimaging due to their higher biocompatibility, safety, and potential for clinical applications compared with those of the inorganic probes. To obtain high‐quality organic dyes, diverse strategies have been taken. In this review, different strategies for optimizing NIR‐II organic fluorophores are summarized, including traditional chemical modifications, and emerging bioengineering operations, which have not previously been elaborated on and summarized. Moreover, the bioengineering strategies are highlighted using endogenous serum proteins and even exogenous gene‐editing proteins, which would provide fresh insights to design good‐performance dyes and help develop NIR‐II probes with clinical translation potential in the future. A critical perspective on the direction of the design strategies of NIR‐II dyes for disease imaging is also proposed.
Augmenting Immunogenic Cell Death and Alleviating Myeloid‐Derived Suppressor Cells by Sono‐Activatable Semiconducting Polymer Nanopartners for Immunotherapy
Authors: Ding Mengbin , Zhang Yijing , Yu Ningyue , Zhou Jianhui , Zhu Liyun , Wang Xing , Li Jingchao 
Published: May 2023

AbstractInducing immunogenic cell death (ICD) by sonodynamic therapy (SDT) is promising for cancer immunotherapy, which however is inefficient due to oxygen depletion that compromises SDT effect and mediates recruitment of immunosuppressive myeloid‐derived suppressor cells (MDSCs). The fabrication of sono‐activatable semiconducting polymer nanopartners (SPNTi) to simultaneously augment ICD and alleviate MDSCs for immunotherapy is reported. A sonodynamic semiconducting polymer, hydrophobic hypoxia‐responsive tirapazamine (TPZ)‐conjugate, and MDSC‐targeting drug (ibrutinib) are encapsulated inside such SPNTi with surface shell of a singlet oxygen (1O2)‐cleavable amphiphilic polymer. TPZ and ibrutinib serve as drug partners to enlarge immunotherapeutic effect. Upon sono‐activation, SPNTi generate 1O2 to break 1O2‐cleavable polymers for in situ liberations of TPZ‐conjugate and ibrutinib in tumor sites, and oxygen is consumed to create severe hypoxic tumor microenvironment, in which, TPZ‐conjugate is activated for augmenting ICD action, while ibrutinib alleviates MDSCs for promoting antitumor immunological effect. In a bilateral tumor mouse model, SPNTi‐mediated sono‐activatable immunotherapy results in growth restraints of primary and distant tumors and noteworthy precaution of tumor metastases. This study thus provides a sono‐activatable immunotherapeutic strategy with high precision and safety for cancer via overcoming post‐treatment hypoxia and targeting MDSCs.
Understanding the Role of Removable Solid Additives: Selective Interaction Contributes to Vertical Component Distributions
Authors: Fan Baobing , Zhong Wenkai , Gao Wei , Fu Huiting , Lin Francis R. , Wong Reese W.‐Y. , Liu Ming , Zhu Chenhui , Wang Cheng , Yip Hin‐Lap , Liu Feng , Jen Alex K.‐Y. 
Published: May 2023

AbstractSequentially deposited organic solar cells (SD‐OSCs) have attracted great attention owing to their ability in achieving a more favorable, vertically phase‐separated morphology to avoid the accumulation of counter charges at absorber/transporting layer interfaces. However, the processing of SD‐OSCs is still quite challenging in preventing the penetration of small‐molecule acceptors into the polymer donor layer via erosion or swelling. Herein, solid additives (SAs) with varied electrostatic potential distributions and steric hinderance are introduced into SD‐OSCs to investigate the effect of evaporation dynamics and selective interaction on vertical component distribution. Multiple modelings indicate that theπ–πinteraction dominates the interactions between aromatic SAs and active layer components. Among them,p‐dibromobenzene shows a stronger interaction with the donor while 2‐chloronaphthalene (2‐CN) interacts more preferably with acceptor. Combining the depth‐dependent morphological study aided by multiple X‐ray scattering methods, it is concluded that the evaporation of SAs can drive the stronger‐interaction component upward to the surface, while having minor impact on the overall molecular packing. Ultimately, the 2‐CN‐treated devices with reduced acceptor concentration at the bottom surface deliver a high power conversion efficiency of 19.2%, demonstrating the effectiveness of applying selective interactions to improve the vertical morphology of OSCs by using SAs with proper structure.
Solid‐State NMR Spectroscopic Investigation of TiO2 Grown on Silica Nanoparticles by Solution Atomic Layer Deposition
Authors: Ding Fei , Tavera Méndez Cindy L. , Grass Jan‐Paul , Crisp Ryan W. , Barr Maïssa K. S. , Wisser Dorothea 
Published: May 2023

AbstractAtomic layer deposition in solution (sALD) is just emerging as a technology for the preparation of thin films. Unlike ALD from the gas phase, it allows for mild reaction conditions in a solvent phase and at room temperature, thus decreasing the energy requirements of the process and widening the range of accessible precursor molecules. In this work, the deposition of thin films of titania on silica is investigated using titanium(IV) isopropoxide (TTIP) and water as precursors, which are alternatingly brought into contact with the support in a home‐built plug flow reactor. The mechanism of covalent grafting of the precursor to the surface, subsequent hydrolysis, and reaction to a layer of titania are investigated in detail using magic angle spinning (MAS) solid‐state nuclear magnetic resonance (NMR) spectroscopy. TTIP preferentially reacts with Q2 groups of condensed silica. 2D solid‐state NMR spectra allow to clearly show the successful grafting of this compound to the support by the appearance of a characteristic signal at −107 ppm, which is tentatively attributed to silicon nuclei in a SiOTi bond, and to reveal the presence of titanol groups on the emerging TiO2 film.
Doping Density Extraction of Plasma Treated Metal Oxide Thin Film Diodes by Capacitance–Voltage Analysis
Authors: Khong Yin Jou , Niang Kham Man , Flewitt Andrew J. 
Published: May 2023

AbstractHigh quality thin film p‐n junction diodes with high rectification ratios and low ideality factors have been fabricated from metal oxides, such as amorphous oxide semiconductors (AOSs), and characterized. Plasma treatment of interfaces has been demonstrated to improve devices made from AOSs, using current–voltage (I–V) measurements. However, capacitance–voltage (C–V) measurements of the devices have been scarcely reported in the literature. Therefore, the focus of this work is characterization of cuprous oxide (Cu2O)/amorphous zinc‐tin oxide (a‐ZTO) thin film heterojunction diodes using C–V analysis. Performance differences of plasma‐treated and untreated diodes that are difficult to observe in I–V analysis are more prominent in C–V analysis. Moreover, C–V analysis allows extraction of charge density profiles, which is a measure of the defect state density that led to intrinsic doping. The variation of doping densities of the untreated diode across the full range of applied reverse bias is shown to be up to 2 orders of magnitude, while those of the treated diodes are within a factor of 10 only. Junction charge profiles, interfacial charge depletion, and accumulation that are key features of rectifying diodes are shown to be clearly distinct between untreated, nitrogen‐treated, and oxygen‐treated diodes, thus explaining why oxygen‐treated diodes are superior.
A Newly Identified Spike Protein Targeted Linear B‐Cell Epitope Based Dissolvable Microneedle Array Successfully Eliciting Neutralizing Activities against SARS‐CoV‐2 Wild‐Type Strain in Mice
Authors: Li Lin , Zhao Zhongpeng , Yang Xiaolan , Su Zhongyi , Li Wendong , Chen Shaolong , Wang Lu , Sun Ting , Du Chen , Li Ziyi , Yang Zeqian , Li Min , Wang Tiecheng , Wang Ying , Fan Yubo , Wang Hui , Zhang Jing 
Published: May 2023

AbstractVaccination is a cost‐effective medical intervention. Inactivated whole virusor large protein fragments‐based severe acute respiratory syndrome coronavirus (SARS‐CoV‐2) vaccines have high unnecessary antigenic load to induce allergenicity and/orreactogenicity, which can be avoided by peptide vaccines of short peptide fragments that may induce highly targeted immune response. However, epitope identification and peptide delivery remain the major obstacles in developing peptide vaccines. Here, a multi‐source data integrated linear B‐cell epitope screening strategy is presented and a linear B‐cell epitope enriched hotspot region is identified in Spike protein, from which a monomeric peptide vaccine (Epitope25) is developed and applied to subcutaneously immunize wildtype BALB/c mice. Indirect ELISA assay reveals specific and dose‐dependent binding between Epitope25 and serum IgG antibodies from immunized mice. The neutralizing activity of sera from vaccinated mice is validated by pseudo and live SARS‐CoV‐2 wild‐type strain neutralization assays. Then a dissolvable microneedle array (DMNA) is developed to pain‐freely deliver Epitope25. Compared with intramuscular injection, DMNA and subcutaneous injection elicit neutralizing activities against SARS‐CoV‐2 wild‐type strain as demonstrated by live SARS‐CoV‐2 virus neutralization assay. No obvious damages are found in major organs of immunized mice. This study may lay the foundation for developing linear B‐cell epitope‐based vaccines against SARS‐CoV‐2.
A Strategy Inspired by the Cicada Shedding Its Skin for Synthesizing the Natural Material NaFe3S5·2H2O
Authors: Dai Hanqing , Dai Wenqing , Chen Yuanyuan , Yan Yukun , Zuo Guangzheng , Hu Zhe , Wei Jinxin , Zhou Wenjie , Zhang Wanlu , Wei Wei , Zhang Guoqi , Guo Ruiqian 
Published: May 2023

AbstractSulfide minerals hold significant importance in both fundamental science and industrial advancement. However, certain natural sulfide minerals, such as NaFe3S5·2H2O (NFS), pose great challenges for exploitation and synthesis due to their high susceptibility to oxidation. To date, no successful precedent exists for synthesizing NFS. Here, a novel approach to synthesizing low‐cost and pollution‐free NFS with high stability using the high‐pressure hydrothermal method based solely on knowledge of its chemical formula is presented. Moreover, an innovative strategy inspired by the cicada's molting process to develop unstable natural materials is proposed. The mechanical, thermal, optical, electrochemical, and magnetic properties of the NFS are thoroughly investigated. The storage of lithium, sodium, and potassium ions is primarily concentrated in the gap between (0 0 1) crystal planes. Additionally, as a catalyst for hydrogen evolution reaction (HER) at 10 mA cm−2, micron‐sized NFS exhibits an excellent overpotential of 6.5 mV at 90 °C, surpassing those of reported HER catalysts of similar size. This research bridges the gap in the sulfide mineral family, overcomes limitations of the high‐pressure hydrothermal method, and paves the way for future synthesis of natural minerals, lunar minerals, and Martian minerals.
Interlayer Electrons Polarization of Asymmetric Metal Nanoclusters/g‐C3N4 for Enhanced Microwave Therapy of Pneumonia
Authors: Li Yuan , Wu Shuilin , Zheng Yufeng , Li Zhaoyang , Cui Zhenduo , Jiang Hui , Zhu Shengli , Liu Xiangmei 
Published: May 2023

AbstractInterlayer interactions in two dimensional (2D) materials promote catalytic performance but often depend on the transport of inter rather than intralayer electrons. In this study, it is found that asymmetric metal‐nanocluster‐doped 2D g‐C3N4 greatly enhances catalytic performance by inducing microwave excitation of interlayer electron delocalization, resulting in a polarization of interlaminar charge transport for microwave disinfection and pneumonia therapy. Asymmetric Fe and Cu nanocluster doping (DCN‐FeCu) enables g‐C3N4 to generate interlayer electrons under microwave irradiation, leading to interlayer polarization processes and electron delocalization effects, thus enhancing the interlayer migration efficiency of electrons. It also improves impurity energy levels and leads to a decrease in work function, allowing DCN‐FeCu to produce microwave carriers across the photoelectric potential barrier under low‐energy microwave radiation (2.45 GHz). This asymmetric doping modulation produces layer number‐dependent microwave electron excitations that are verified using multi‐metal doping. Therefore, structurally modulated asymmetric doping of 2D materials with interfacial spatial effects can provide efficient microwave disinfection and pneumonia therapy.
Dry Pre‐Lithiation for Graphite‐Silicon Diffusion‐Dependent Electrode for All‐Solid‐State Battery
Authors: Lee Jongjun , Jin Dahee , Kim Ju Young , Roh Youngjoon , Lee Hyobin , Kang Seok Hun , Choi Jaecheol , Jo Taejin , Lee Young‐Gi , Lee Yong Min 
Published: May 2023

AbstractThe graphite/silicon‐based diffusion‐dependent electrodes (DDEs) are one of the promising electrode designs to realize high energy density for all‐solid‐state batteries (ASSBs) beyond conventional composite electrode design. However, the graphite/silicon‐based electrode also suffers from large initial irreversible capacity loss and capacity fade caused by significant volume change during cycling, which offsets the advantages of the DDEs in ful‐cell configuration. Herein, a new concept is presented for DDEs, dry pre‐lithiated DDEs (PL‐DDEs) by introducing Li metal powder. Since Li metal powder provides Li ions to graphite and silicon even in a dry state, the lithiation states of active materials is increased. Moreover, the residual Li within PL‐DDE further serves as an activator and a reservoir for promoting the lithiation reaction of the active materials and compensating for the active Li loss upon cycling, respectively. Based on these merits, ASSBs with PL‐DDE exhibit excellent cycling performance with higher columbic efficiency (85.2% retention with 99.6% CE at the 200th cycle) compared to bare DDE. Therefore, this dry lithiation process must be a simple but effective design concept for DDEs for high‐energy‐density ASSBs.
Comprehensive Battery Safety Risk Evaluation: Aged Cells versus Fresh Cells Upon Mechanical Abusive Loadings
Authors: Jia Yikai , Gao Xiang , Ma Lin , Xu Jun 
Published: May 2023

AbstractDespite their wide applications, lithium‐ion batteries (LIBs) have been struggling with their safety risks arising from different lifetime stages. Here, the NCMA pouch cell is taken as an example, and the safety of both fresh and aged cells from three milestone stages, that is, internal short circuit (ISC) triggering risk, ISC mode, and the subsequent thermal runaway (TR) consequence is investigated. By combining mechanical abusive testing and physics‐based models on commercialized cells with various states‐of‐health (SOH) and states‐of‐charge, it is discovered that the ISC triggering delays with the decay of SOH and soft ISC mode will be triggered more frequently, which is mainly due to the mechanical behaviors of the current collectors. The temperature rises and peak temperature during the subsequent TR also become milder for aged cells due to the reduced capacity and deterministic soft ISC process. Results here provide a mechanistic explanation of the safety risk comparison between the fresh and aged cells, offering cornerstone guidance to the evaluation and design of next‐generation safer LIBs.
Transformed Solvation Structure of Noncoordinating Flame‐Retardant Assisted Propylene Carbonate Enabling High Voltage Li‐Ion Batteries with High Safety and Long Cyclability
Authors: Lu Di , Zhang Shenghang , Li Jiedong , Huang Lang , Zhang Xiaohu , Xie Bin , Zhuang Xiangchun , Cui Zili , Fan Xiulin , Xu Gaojie , Du Xiaofan , Cui Guanglei 
Published: May 2023

AbstractThe evolution of high‐energy‐density lithium‐ion batteries (LIBs) urgently requires the development of high‐safety electrolytes with high voltage resistance. Here, noncoordinating flame retardant pentafluoro‐(phenoxy)‐cyclotriphosphazene (FPPN) endows propylene carbonate (PC, 70 vol%)‐based electrolytes with high graphite anode compatibility, non‐flammability, high voltage stability, and excellent separator/electrode wettability. Theoretical calculations reveal that FPPN significantly affects Li+‐PC‐anion interactions and favors Li+ desolvation. Based on in situ optical microscopy and in situ differential electrochemical mass spectrometry, it is innovatively proposed that large amounts of H2 and C3H6 from PC decomposition play a dominant role in destroying the graphitic structure. The evolution of H2 and C3H6 is dramatically alleviated and totally suppressed, respectively, when FPPN prevents PC‐induced graphite exfoliation. More encouragingly, an optimized PC/FPPN‐based electrolyte (70 vol% PC) enables a high voltage LiCoO2/graphite pouch cell (4.35 V, ≈2.6 Ah, ≈242 Wh kg−1) with excellent cycle life and high safety. This work deepens the understanding of PC‐graphite compatibility and opens a new avenue of realizing practical application of PC‐based electrolytes (PC content over 50 vol%) in high capacity (over 2 Ah) LIBs.
Long‐Life and High‐Loading All‐Solid‐State Li–S Batteries Enabled by Acetylene Black with Dispersed Co‐N4 as Single Atom Catalyst
Authors: Zhong Haoyue , Su Yu , Wu Yuqi , Gu Jiabao , Ma Ruqin , Luo Yu , Lin Hongxin , Tao Mingming , Chen Jingzhao , Liang Ziteng , Wang Kangjun , Zheng Xuefan , Chen Zirong , Peng Jinxue , Lv Zhongwei , Gong Zhengliang , Huang Jianyu , Yang Yong 
Published: May 2023

AbstractAll‐solid‐state Li–S batteries (ASSLSBs) have exhibited great promise as next‐generation energy storage systems due to the elimination of the shuttle effect and flammability. However, the low reactivity of sulfur and poor solid–solid contact in the composite cathode result in limited electrochemical performances. Here, a Co‐N4‐decorated carbon composite is prepared by direct ball milling and serves as a sulfur host for ASSLSBs. The uniform distribution of Co‐N4 can effectively accelerate the redox conversion of sulfur and inhibit the agglomeration of sulfur particles during cycling through strong chemical affinity. Benefiting from these merits, the sulfur cathode with a sulfur content of 40% and a sulfur loading of 1.5 mg cm−2 in ASSLSBs exhibits high reversible capacity (1439 mAh g−1 at 0.1 C) and superior long‐term cyclic performance (capacity fade rate of 0.025% per cycle for 1000 cycles at 0.5 C). Even under a sulfur loading up to 4.5 mg cm−2, the areal capacity can reach 5.13 mAh cm−2 at 60 °C and maintain stable cycling over 300 cycles at 0.3 C. This work offers a promising strategy for enhancing the electrochemical performance of ASSLSBs.