bluuebunny/crossref_metadata_2025_split huggingface dataset:
Self‐Adjustment of Intrinsic Reaction Intermediate on Atomically Dispersed Co2–N6 Binuclear Sites Achieving Boosted Electrocatalytic Oxygen Reduction Performance
Authors: Lu Tingyu , Zhou Qixing , Li Jing , Li Tongfei , Gong Jiayue , Zhang Songtao , Pang Huan , Xi Shibo , Xu Lin , Luo Gan , Sun Dongmei , Sun Kang , Tang Yawen 
Published: May 2024

AbstractIsolated dual‐atom catalysts (DACs) have sparked enormous research enthusiasm in new energy community due to their great potentials to substitute the state‐of‐the‐art Pt‐based catalysts. Nevertheless, explicitly unraveling the underlying catalytic mechanisms is of critical significance for performance enhancement, yet remains a huge challenge. Herein, the study reports a reliable hard template‐mediated strategy to accomplish the construction of atomically isolated binuclear Co2‐N6 sites stabilized by ultrathin hollow carbon nanospheres (abbreviated as Co2‐DAs@CHNSs). Systematic spectroscopy characterization and theoretic calculations uncover that the Co2‐N6 sites follow a self‐adjusting mechanism caused by the intrinsic OH intermediate. The involvement of the ‐OH energy‐level modifier is found to induce the electron redistribution and alternation of antibonding orbital fillings for the generated Co2‐N6‐OH site, leading to reduced potential‐determining step (PDS) energy barrier, and thus boosted intrinsic activity. Consequently, the well‐managed Co2‐DAs@CHNSs afford outstanding oxygen reduction reaction (ORR) activity with a half‐wave potential of 0.87 V in alkaline electrolyte, overmatching the Pt benchmark. Furthermore, the Co2‐DAs@CHNSs‐assembled aqueous and all‐solid‐state rechargeable zinc–air batteries (ZABs) demonstrate high power density, large specific capacity, and robust stability. The findings offer an innovative avenue to rationally manipulate the electronic structures of active sites for DACs via a powerful self‐ligand modification strategy.
Defect‐Expedited Photocarrier Separation in Zn2In2S5 for High‐Efficiency Photocatalytic C─C Coupling Synchronized with H2 Liberation from Benzyl Alcohol
Authors: Ma Minmin , Wang Ran , Shi Li , Li Ronghua , Huang Jie , Li Zhuo , Li Peng , Konysheva Elena Yu. , Li Yanbo , Liu Gang , Xu Xiaoxiang 
Published: May 2024

AbstractPhotocatalytic carbon‐carbon (C─C) coupling of benzyl alcohol is a promising means to coproduce the value‐added chemicals with H2 but is generally subject to low efficiency in terms of photon utilization. Here, efficient benzyl alcohol C─C coupling is achieved over Zn2In2S5 containing a tunable content of Zn vacancies (VZn). The VZn tends to form shallow defect states below the conduction band that can expedite photocarrier separation by collecting the photo‐generated electrons. The VZn‐collected electrons are essential for a high selectivity of the C─C coupling reactions because they enable a fast elimination of the byproduct benzaldehyde by catalyzing its reduction back to the ketyl radicals. Under simulated sunlight, the VZn‐containing Zn2In2S5 accomplishes ≈100% conversion of benzyl alcohol for merely 1 h and attains ≈100% selectivity for the C─C coupling compounds for 2 h, delivering an apparent quantum yield as high as 7.7% at 420 ± 20 nm. The benefits of VZn have also been verified by the theoretical calculations that indicate reduced energy barriers for various surface reactions in the presence of VZn. This work brings fresh mechanistic insights into the role of VZn and can serve as a useful guideline in the design of efficient photocatalysts.
A Cyanine with 83.2% Photothermal Conversion Efficiency and Absorption Wavelengths over 1200 nm for Photothermal Therapy
Authors: Zhao Liang , Zhu Han , Duo You‐Yang , Wang Zhi‐Gang , Pang Dai‐Wen , Liu Shu‐Lin 
Published: May 2024

AbstractDeveloping small‐molecule photothermal agents (PTAs) with good near‐infrared‐II (NIR‐II) response for deeper tissue penetration and minimizing damage to healthy tissues has attracted much attention in photothermal therapy (PTT). However, concentrating ultra‐long excitation wavelengths and high photothermal conversion efficiencies (PCEs) into a single organic small molecule is still challenging due to the lack of suitable molecular structures. Here, six polymethine cyanine molecules based on the structure of indocyanine green are synthesized by increasing the conjugated structure of the two‐terminal indole salts and the number of rigid methine units, and incorporating longer alkyl side chains into the indole salts. Ultimately, IC‐1224 is obtained with an absorption wavelength of more than 1200 nm, which has a high PCE up to 83.2% in the NIR‐II window and exhibits excellent PTT tumor ablation performance. This provides a high‐performance NIR‐II‐responsive PTA, and offers further possibilities for the application of PTT in biomedical fields.
Reprograming Clots for In Vivo Chemical Targeting in Traumatic Brain Injury
Authors: Kandell Rebecca M. , Wu Jason R. , Kwon Ester J. 
Published: May 2024

AbstractTraumatic brain injury (TBI) is a critical public health concern, yet there are no therapeutics available to improve long‐term outcomes. Drug delivery to TBI remains a challenge due to the blood‐brain barrier and increased intracranial pressure. In this work, a chemical targeting approach to improve delivery of materials to the injured brain, is developed. It is hypothesized that the provisional fibrin matrix can be harnessed as an injury‐specific scaffold that can be targeted by materials via click chemistry. To accomplish this, the brain clot is engineered in situ by delivering fibrinogen modified with strained cyclooctyne (SCO) moieties, which incorporated into the injury lesion and is retained there for days. Improved intra‐injury capture and retention of diverse, clickable azide‐materials including a small molecule azide‐dye, 40 kDa azide‐PEG nanomaterial, and a therapeutic azide‐protein in multiple dosing regimens is subsequently observed. To demonstrate therapeutic translation of this approach, a reduction in reactive oxygen species levels in the injured brain after delivery of the antioxidant catalase, is achieved. Further, colocalization between azide and SCO‐fibrinogen is specific to the brain over off‐target organs. Taken together, a chemical targeting strategy leveraging endogenous clot formation is established which can be applied to improve therapeutic delivery after TBI.
Passivation Layers in Mg‐Metal Batteries: Robust Interphases for Li‐Metal Batteries
Authors: Zhao Zhiming , Nian Binbin , Lei Yongjiu , Zhao Lingyun , Hedhili Mohamed N. , Guo Dong , Shi Zixiong , Zhao Wenli , El‐Demellawi Jehad K. , Wang Yizhou , Zhu Yunpei , Xu Kang , Alshareef Husam N. 
Published: May 2024

AbstractIn advanced batteries, interphases serve as the key component in stabilizing the electrolyte with reactive electrode materials far beyond thermodynamic equilibria. While an active interphase facilitates the transport of working ions, an inactive interphase obstructs ion flow, constituting the primary barrier to the realization of battery chemistries. Here, a successful transformation of a traditionally inactive passivating layer on Mg‐metal anode, characteristic of Mg‐metal batteries with typical carbonate electrolytes, into an active and robust interphase in the Li‐metal scenario is presented. By further strategically designing magnesiated Li+ electrolytes, the in situ development of this resilient interphase on Li‐metal anodes, imparting enduring stability to Li‐metal batteries with nickel‐rich cathodes is induced. It is identified that the strong affinity between Mg2+ and anions in magnesiated Li+ electrolytes assembles ionic clusters with a bias for reducibility, thereby catalyzing the creation of anion‐derived interphases rich in inorganic constituents. The prevalence of ionic clusters induced by magnesiation of electrolytes has brought properties only available in high‐concentration electrolytes, suggesting a fresh paradigm of tailing electrolytes for highly reversible LMBs.
Multi‐Interface Engineering of MXenes for Self‐Powered Wearable Devices
Authors: Liu Chao , Feng Ziheng , Yin Tao , Wan Tao , Guan Peiyuan , Li Mengyao , Hu Long , Lin Chun‐Ho , Han Zhaojun , Xu Haolan , Cheng Wenlong , Wu Tom , Liu Guozhen , Zhou Yang , Peng Shuhua , Wang Chun , Chu Dewei 
Published: May 2024

AbstractSelf‐powered wearable devices with integrated energy supply module and sensitive sensors have significantly blossomed for continuous monitoring of human activity and the surrounding environment in healthcare sectors. The emerging of MXene‐based materials has brought research upsurge in the fields of energy and electronics, owing to their excellent electrochemical performance, large surface area, superior mechanical performance, and tunable interfacial properties, where their performance can be further boosted via multi‐interface engineering. Herein, a comprehensive review of recent progress in MXenes for self‐powered wearable devices is discussed from the aspects of multi‐interface engineering. The fundamental properties of MXenes including electronic, mechanical, optical, and thermal characteristics are discussed in detail. Different from previous review works on MXenes, multi‐interface engineering of MXenes from termination regulation to surface modification and their impact on the performance of materials and energy storage/conversion devices are summarized. Based on the interfacial manipulation strategies, potential applications of MXene‐based self‐powered wearable devices are outlined. Finally, proposals and perspectives are provided on the current challenges and future directions in MXene‐based self‐powered wearable devices.
A Cable‐Stayed Honeycomb Superstructure to Improve the Stability of Li‐Rich Materials via Inhibiting Interlaminar Lattice Strain
Authors: Jiang Yun‐shan , Liao Zhong‐miao , Yu Fu‐da , Ke Wang , Li Xin‐yu , Xia Yang , Xu Gui‐jing , Sun Gang , Xia Yuan‐guang , Yin Wen , Deng Liang , Zhao Lei , Wang Zhen‐bo 
Published: May 2024

AbstractIn layered Li‐rich materials, over stoichiometric Li forms an ordered occupation of LiTM6 in transition metal (TM) layer, showing a honeycomb superstructure along [001] direction. At the atomic scale, the instability of the superstructure at high voltage is the root cause of problems such as capacity/voltage decay of Li‐rich materials. Here a Li‐rich material with a high Li/Ni disorder is reported, these interlayer Ni atoms locate above the honeycomb superstructure and share adjacent O coordination with honeycomb TM. These Ni─O bonds act as cable‐stayed bridge to the honeycomb plane, and improve the high‐voltage stability. The cable‐stayed honeycomb superstructure is confirmed by in situ X‐ray diffraction to have a unique cell evolution mechanism that it can alleviate interlaminar lattice strain by promoting in‐plane expansion along a‐axis and inhibiting c‐axis stretching. Electrochemical tests also demonstrate significantly improved long cycle performance after 500 cycles (86% for Li‐rich/Li half cell and 82% for Li‐rich/Si‐C full cell) and reduced irreversible oxygen release. This work proves the feasibility of achieving outstanding stability of lithium‐rich materials through superstructure regulation and provides new insights for the development of the next‐generation high‐energy‐density cathodes.
Gradient Doping Enables an Extraordinary Efficiency in Thermoelectric PbTe1−xIx
Authors: Zhou Jiayu , Chen Zhiwei , Luo Jun , Li Wen , Pei Yanzhong 
Published: May 2024

AbstractThe conversion efficiency of thermoelectric generators that have to be operated under a temperature difference (ΔT) is mainly determined by material's dimensionless figure of merit (zT). However, maximization of zT at each temperature requires an optimization of carrier concentration (nopt) which strongly depends on the temperature and band parameters. Commonly utilized strategy of chemical doping usually enables a homogeneous carrier concentration throughout the material, leading the maximal zT to be achievable only within a narrow temperature range. In this work, a gradiently doping is successfully realized in PbTe1−xIx using a vertical gradient solidification technique, enabling a spatial gradient in carrier concentration that correspondingly optimizes zT at each portion of the material under its operating temperature. Such a gradient doping results in an extraordinary device efficiency of ≈14% at a ΔT of ≈500 K, corresponding to a ≈40% improvement as compared to that of homogeneous doping. Since directional solidification technique commonly enables gradient dopant concentrations in semiconductors, the resultant gradient carrier concentration is illustrated here as an effective approach for advancing thermoelectrics.
Can Pressure be a Good Strategy for Optimizing Thermoelectric Performance of SnPS3${\rm SnPS}_3$?
Authors: Sharma Gautam , Singh Nirpendra 
Published: May 2024

AbstractExternal pressure can significantly alter the transport coefficients, power factor, and figure of merit because of its direct influence on the electronic structure, electron–phonon, and phonon–phonon couplings. This study delves into the electronic and thermal transport properties of at external pressures up to 30 GPa using first‐principles calculations and Boltzmann transport theory. The electron–phonon relaxation time is computed within the electron–phonon‐averaged (EPA) approximation, enabling exploration beyond the constant relaxation time approximation. The first‐principles calculations reveal an indirect bandgap of 1.76 (without pressure) and 0.12 eV (30 GPa). The density functional perturbation theory calculations confirm the dynamic stability of at external pressure up to 30 GPa. The electronic transport properties are improved by more than one order of magnitude at 30 GPa, consistent with experimental observations. The Peierls–Boltzmann transport calculations demonstrate the room temperature lattice thermal conductivity of 0.22 (without pressure) and 7.4 (at 30 GPa). The results emanate that exhibits of 0.71 at 900 K at a hole doping of 2 at zero pressure, which decreases with increasing pressure. The findings explore the effect of external pressure on both electronic and thermal transport properties of , warranting further experimental exploration of thermal transport properties at higher pressures.
Control of Ferroelectricity in Solution‐Processed Hafnia Films Through Annealing Atmosphere
Authors: Mandal Barnik , Valle Nathalie , Adib Brahime El , Girod Stéphanie , Menguelti Kevin , Fleming Yves , Grysan Patrick , Defay Emmanuel , Glinsek Sebastjan 
Published: May 2024

AbstractChemical Solution Deposition enables low‐cost fabrication of ferroelectric HfO2 films suitable for piezoelectric applications. Control of processing parameters is of utmost importance to obtain high‐quality functional films. However, the impact of the annealing atmosphere on ferroelectric properties of solution‐processed HfO2 films is not clear. In this work, the influence of annealing atmosphere and growth methods on orientation, density and electrical properties of La:HfO2 films is studied. The 45 nm‐thick films are grown by two routes, conventional (crystallization of the final 45 nm‐thick film) and layer‐by‐layer (intermediate crystallizations of 5 nm‐thick films). Annealing is performed in N2:O2 and Ar atmosphere. Films grown by layer‐by‐layer method in an oxygen‐rich atmosphere tend to have higher density (87% of theoretical density) and remanent polarization (15 µC cm–2) than the conventional films (density and remanent polarization of 80% and 7.5 µC cm‐2). Secondary ion mass spectrometry reveals higher amounts of carbon presence in the conventional films annealed in Ar. For layer‐by‐layer films, the ability to control the preferential out‐of‐plane orientation from (111) to (002) simply by changing the annealing atmosphere, is demonstrated. The results can guide the path toward high‐quality thicker films for piezoelectric applications.
Controllable Electrical Properties of ZrO2/BiFeO3 Bilayer Memristor from Synaptic Mimic to TRNG Circuit Application by Modulating Compliance Currents
Authors: Jin Yaoyao , Zhu Ming , Zhou Yuhong , Zhang Zihao , Wang Jinzhao , Song Xingjuan , Meng Jiahao , Ke Shanwu , Zhang Tianyi , Chen Siqi , Li Ruiqi , Jiang Bei , Ye Cong 
Published: May 2024

AbstractApart from simulating biological synapses, memristors can also be used in the secure encryption by exploiting their inherent random resistive switching (RS) properties. In this work, nonvolatile Ta/BiFeO3/ZrO2/Pt memristor is fabricated with 2 nm inserting BiFeO3 layer. At a high compliance current of 10 mA, it presents gradual RS characteristics during the set process, which resulting in 30 conductance states. Synaptic behavior can be successfully mimicked by precise conductance modulating under pulse electrical stimulation. Whereas under a low compliance current of 500 µA, it exhibits abrupt RS behavior, and the set voltage ranged from 0.3–0.8 V, which can be effectively as an entropy source for true random number generator (TRNG). Due to its Shannon entropy of 300 bits is 0.99987, Hamming weights and intra‐Hamming distances tend to be 50%. Furthermore, the software simulation of encryption and decryption of cat image is achieved by combining the key generated by TRNG. The controllable electrical properties of the Ta/BiFeO3/ZrO2/Pt device can be modulated by the compliance current, thus meeting the computing or safety requirements, which provides a solid foundation for the development of integrating computation and security at the hardware level.
Determination and Engineering of Li‐Ion Tortuosity in Electrode Toward High Performance of Li‐Ion Batteries
Authors: Yan Ziwen , Wang Li , Zhang Hao , He Xiangming 
Published: May 2024

AbstractWith the progressively widespread application of lithium‐ion batteries, their energy density and power density are being pursued to the extremely high. However, both cannot be reached simultaneously at present. Tortuosity depicts the relationship in ionic diffusion between bulk electrolyte and the electrolyte in a porous electrode, provides information about channels within electrodes, and correlates the current dilemma between energy density and power capability of the lithium‐ion batteries. It is crucial to upgrade the fast charging and discharging performance of LIBs electrodes without losing volumetric energy density and using tortuosity as a guide is able to achieve this goal fundamentally. Meanwhile, tortuosity can serve as an evaluation parameter for production quality assessment, but this demands a fast, accurate, and cost‐effective measuring method. After the definition and measurement of tortuosity are provided, this article analyzes the structural influencing factors of tortuosity which have impacts on ion transportation and subsequently on tortuosity to facilitate a more systematic and comprehensive picture. Through the discussion of contradictions and influencing factors, a more refined transmission line model (the refined TLM) is perceived as the very first step to drive both aforementioned goals toward success and is discussed in the perspective part.
Tailoring Electrochemical Water Oxidation Activity from the Isostructural Series of Alkaline‐Stable Bimetallic Fe,Ni‐Azolate Metal–Organic Frameworks
Authors: Kim Minseok , Jeong Jaewoo , Kim Dong Hyun , Park Geunchan , Yi Jaekyung , Kim Sinhyeop , Kim Hyungjun , Choi Chang Hyuck , Shin Hyeyoung , Park Sarah S. 
Published: May 2024

AbstractIncorporating electrocatalytic active sites into the reticular framework allows for the design of novel catalytic structures promoting desired catalytic reactions with efficient mass transfer. However, to fully exploit the advantages of such a framework, it is crucial to ensure the electrochemical stability of the material. In this context, alkaline‐stable bimetallic MxNi2‐xCl2BTDD (M = Fe, Co) metal–organic frameworks (MOFs) are employed as electrocatalysts for alkaline water oxidation reaction (WOR) to understand the correlation between secondary metal incorporation and catalytic activity changes. For a specific Fe ratio within the MOF, the optimal catalytic activity is achieved at an overpotential of 315 mV at a WOR current density of 10 mA cm−2geo. Based on its well‐defined crystal structure and uniformly arranged metal nodes, which are not limited to specific facets, the cooperative electrocatalytic mechanism during the faradaic WOR process is investigated through operando Raman spectroscopy and density functional theory calculations. These results enable the interpretation of the electrochemical WOR mechanism based on MOF, providing a further fundamental understanding of electrocatalytic activity in bimetallic systems.
Peripheral blood stem cell versus bone marrow graft for patients ≥60 years undergoing reduced intensity conditioning haploidentical transplantation for acute myeloid leukemia in complete remission: An analysis of the Acute Leukemia Working Party of the European Society for Blood and Marrow Transplantation
Authors: Devillier Raynier , Galimard Jacques‐Emmanuel , Blaise Didier , Raiola Anna Maria , Bramanti Stefania , Grillo Giovanni , Pastano Rocco , de Latour Régis Peffault , Busca Alessandro , López‐Corral Lucía , Rodríguez Arancha Bermúdez , Schmid Christoph , Forcade Edouard , Vydra Jan , Solano Carlos , Bug Gesine , Neubauer Andreas , Charbonnier Amandine , Brissot Eolia , Nagler Arnon , Ciceri Fabio , Mohty Mohamad 
Published: May 2024

AbstractIn the context of T‐cell replete haploidentical stem cell transplantation (Haplo‐SCT) using post‐transplantation cyclophosphamide (PT‐Cy), it is still unknown whether peripheral blood (PB) or bone marrow (BM) is the best graft source. While PB is associated with a higher incidence of graft‐versus‐host disease (GVHD), it may induce a stronger graft‐versus‐leukemia effect compared to BM, notably in acute myeloid leukemia (AML). From the EBMT registry database, we compared T‐cell replete PB (n = 595) versus BM (n = 209) grafts in a large cohort of 804 patients over the age of 60 years who underwent Haplo‐SCT with PT‐Cy for an AML in first or second complete remission. The risk of acute GVHD was significantly higher in the PB group (Grade II‐IV: HR = 1.67, 95% CI [1.10–2.54], p = 0.01; Grade III‐IV: HR = 2.29, 95% CI [1.16–4.54], p = 0.02). No significant difference was observed in chronic GVHD or non‐relapse mortality. In the PB group, the risk of relapse was significantly lower in the PB group (HR = 0.65, 95% CI [0.45–0.94], p = 0.02) and leukemia‐free survival was significantly better (HR = 0.76, 95% CI [0.59–0.99], p = 0.04), with a trend toward better overall survival (HR = 0.78, 95% CI [0.60–1.01], p = 0.06). We conclude that in the specific context of Haplo‐SCT with PT‐Cy, PB grafts represent a valid option to decrease the risk of relapse and improve outcome of older AML patients who usually do not benefit from conditioning intensification.