bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reinforcing the Electrode/Electrolyte Interphases of Lithium Metal Batteries Employing Locally Concentrated Ionic Liquid Electrolytes
Authors: Liu Xu , Mariani Alessandro , Diemant Thomas , Di Pietro Maria Enrica , Dong Xu , Mele Andrea , Passerini Stefano 
Published: November 2023

AbstractLithium metal batteries (LMBs) with nickel‐rich cathodes are promising candidates for next‐generation high‐energy‐density batteries, but the lack of sufficiently protective electrode/electrolyte interphases (EEIs) limits their cyclability. Herein, trifluoromethoxybenzene is proposed as a cosolvent for locally concentrated ionic liquid electrolytes (LCILEs) to reinforce the EEIs. With a comparative study of a neat ionic liquid electrolyte (ILE) and three LCILEs employing fluorobenzene, trifluoromethylbenzene, or trifluoromethoxybenzene as cosolvents, it is revealed that the fluorinated groups tethered to the benzene ring of the cosolvents not only affect the electrolytes’ ionic conductivity and fluidity, but also the EEIs’ composition via adjusting the contribution of the 1‐ethyl‐3‐methylimidazolium cation (Emim+) and bis(fluorosulfonyl)imide anion. Trifluoromethoxybenzene, as the optimal cosolvent, leads to a stable cycling of LMBs employing 5 mAh cm−2 lithium metal anodes (LMAs), 21 mg cm−2 LiNi0.8Co0.15Al0.05 (NCA) cathodes, and 4.2 µL mAh−1 electrolytes for 150 cycles with a remarkable capacity retention of 71%, thanks to a solid electrolyte interphase rich in inorganic species on LMAs and, particularly, a uniform cathode/electrolyte interphase rich in Emim+‐derived species on NCA cathodes. By contrast, the capacity retention under the same condition is only 16%, 46%, and 18% for the neat ILE and the LCILEs based on fluorobenzene and benzotrifluoride, respectively.
Adaptive Neural Activation and Neuromorphic Processing via Drain‐Injection Threshold‐Switching Float Gate Transistor Memory
Authors: Wang Han , Lu Yuanlong , Liu Shangbo , Yu Jun , Hu Man , Li Sainan , Yang Rui , Watanabe Kenji , Taniguchi Takashi , Ma Ying , Miao Xiangshui , Zhuge Fuwei , He Yuhui , Zhai Tianyou 
Published: November 2023

AbstractHetero‐modulated neural activation is vital for adaptive information processing and learning that occurs in brain. To implement brain‐inspired adaptive processing, previously various neurotransistors oriented for synaptic functions are extensively explored, however, the emulation of nonlinear neural activation and hetero‐modulated behaviors are not possible due to the lack of threshold switching behavior in a conventional transistor structure. Here, a 2D van der Waals float gate transistor (FGT) that exhibits steep threshold switching behavior, and the emulation of hetero‐modulated neuron functions (integrate‐and‐fire, sigmoid type activation) for adaptive sensory processing, are reported. Unlike conventional FGTs, the threshold switching behavior stems from impact ionization in channel and the coupled charge injection to float gate. When a threshold is met, a sub‐30 mV dec−1increase of transistor conductance by more than four orders is triggered with a typical switch time of approximately milliseconds. Essentially, by feeding light sensing signal as the modulation input, it is demonstrated that two typical tasks that rely on adaptive neural activation, including collision avoidance and adaptive visual perception, can be realized. These results may shed light on the emulation of rich hetero‐modulating behaviors in biological neurons and the realization of biomimetic neuromorphic processing at low hardware cost.
Self‐Powered Temperature Electronic Skin Based on Island‐Bridge Structure and Bi‐Te Micro‐Thermoelectric Generator for Distributed Mini‐Region Sensing
Authors: Kang Man , Qu Ruixiang , Sun Xiaowen , Yan Yuedong , Ma Zhijun , Wang He , Yan Kaifen , Zhang Weifeng , Deng Yuan 
Published: November 2023

AbstractThermoelectric (TE) effect based temperature sensor can accurately convert temperature signal into voltage without external power supply, which have great application prospects in self‐powered temperature electronic skin (STES). But the fabrication of stretchable and distributed STES still remains a challenge. Here, a novel STES design strategy is proposed by combining flexible island‐bridge structure with BiTe‐based micro‐thermoelectric generator (µ‐TEG). Furthermore, a 4 × 4 vertical temperature sensor array with good stretchability and distributed sensing property has been fabricated for the first time. The interfacial chemical bonds located between the rigid islands (µ‐TEG) and the flexible substrate (polydimethylsiloxane, PDMS) endow the STES with excellent stretchability, and its sensing performance remains unchanged under 30% strain (the maximum strain of human skin). Moreover, the STES sensing unit possesses high sensitivity (729 µV K−1), rapid response time (0.157 s), and high spatial resolution (2.75 × 2.75 mm2). As a proof of concept, this work demonstrates the application of the STES in the detection of mini‐region heat sources in various scenarios including noncontact spatial temperature responsing, intelligent robotic thermosensing, and wearable temperature sensing. Such an inspiring design strategy is expected to provide guidance for the design and fabrication of wearable self‐powered temperature sensors.
Gradient Structural and Compositional Design of Conductive MXene Aerogels for Stable Zn Metal Anodes
Authors: Li Yang , Pang Zhenqian , Ghani Awais , Little Joshua M. , Wang Liping , Yang Haochen , Zhao Yusheng , Chen Po‐Yen 
Published: November 2023

AbstractAqueous rechargeable zinc‐ion batteries (ZIBs) are a safe and low‐cost energy storage technology. However, practical ZIB exploitation faces critical challenges in achieving stable Zn metal anodes, which suffer from hydrogen evolution reaction (HER) corrosion and Zn dendrite growth. To address these challenges, a Zn2+‐induced assembly process to fabricate Ti3C2Tx MXene‐reduced graphene oxide aerogels with ZnO crust layers on Zn plates (abbreviated as ZnO/MG aerogel–Zn) that serve as stable Zn metal anodes is reported. By applying a constant voltage to a Zn plate, Zn2+ is gradually released to ionically crosslink MG nanosheets. After spontaneous hydrolysis and freeze‐drying, a crust layer composed of ZnO nanoparticles is in situ formed. Additionally, the gradient Zn−O/Zn−F profiles across the ZnO/MG aerogel can facilitate Zn2+ transport and collectively suppress HER, enabling fast electrochemical kinetics and dendrite‐free Zn deposition. Symmetric cells with ZnO/MG aerogel–Zn electrodes present stable cycling for 1200 h at 10 mA cm−2, and full cells achieve long lifespans at high rates (>500 cycles at 1.0 A g−1). Combining the advantages of an insulating protective layer and a conductive structured host, the ZnO/MG aerogel–Zn electrode with gradient structures and compositions creates synergistic advances in stable Zn metal anodes.
Smart Dope: A Self‐Driving Fluidic Lab for Accelerated Development of Doped Perovskite Quantum Dots
Authors: Bateni Fazel , Sadeghi Sina , Orouji Negin , Bennett Jeffrey A. , Punati Venkat S. , Stark Christine , Wang Junyu , Rosko Michael C. , Chen Ou , Castellano Felix N. , Reyes Kristofer G. , Abolhasani Milad 
Published: November 2023

AbstractMetal cation‐doped lead halide perovskite (LHP) quantum dots (QDs) with photoluminescence quantum yields (PLQYs) higher than unity, due to quantum cutting phenomena, are an important building block of the next‐generation renewable energy technologies. However, synthetic route exploration and development of the highest‐performing QDs for device applications remain challenging. In this work, Smart Dope is presented, which is a self‐driving fluidic lab (SDFL), for the accelerated synthesis space exploration and autonomous optimization of LHP QDs. Specifically, the multi‐cation doping of CsPbCl3 QDs using a one‐pot high‐temperature synthesis chemistry is reported. Smart Dope continuously synthesizes multi‐cation‐doped CsPbCl3 QDs using a high‐pressure gas‐liquid segmented flow format to enable continuous experimentation with minimal experimental noise at reaction temperatures up to 255°C. Smart Dope offers multiple functionalities, including accelerated mechanistic studies through digital twin QD synthesis modeling, closed‐loop autonomous optimization for accelerated QD synthetic route discovery, and on‐demand continuous manufacturing of high‐performing QDs. Through these developments, Smart Dope autonomously identifies the optimal synthetic route of Mn‐Yb co‐doped CsPbCl3 QDs with a PLQY of 158%, which is the highest reported value for this class of QDs to date. Smart Dope illustrates the power of SDFLs in accelerating the discovery and development of emerging advanced energy materials.
Multi‐Shell Copper Catalysts for Selective Electroreduction of CO2to Multicarbon Chemicals
Authors: Xiao Yukun , Wang Meng , Yang Haozhou , Qiu Haoran , Lu Haotian , Da Yumin , Chen Ganwen , Jiang Tianyuan , Fu Weiwei , Hu Bihao , Chen Junmei , Chen Lei , Ding Yishui , Cui Baihua , Jiang Chonglai , Sun Zejun , Long Yu , Yang Haotian , Tian Zhangliu , Wang Lei , Chen Wei 
Published: November 2023

AbstractElectrocatalytic CO2reduction (CO2R) coupled with renewable electricity has been considered as a promising route for the sustainability transition of energy and chemical industries. However, the unsatisfactory yield of desired products, particularly multicarbon (C2+) products, has hindered the implementation of this technology. This work describes a strategy to enhance the yield of C2+product formation in CO2R by utilizing spatial confinement effects. The finite element simulation results suggest that increasing the number of shells in the catalyst wil lead to a high local concentration of *CO and promotes the formation of C2+products. Inspired by this, Cu nanoparticles are synthesized with desired hollow multi‐shell structures. The CO2reduction results confirm that as the number of shells increase, the hollow multi‐shell copper catalysts exhibit improved selectivity toward C2+products. Specifically, the Cu catalyst with 4.4‐shell achieved a high selectivity of over 80% toward C2+at a current density of 900 mA cm−2. Evidence from in situ attenuated total reflection surface‐enhanced infrared absorption spectroscopy unveils that the multi‐shell Cu catalyst exhibits an enhanced *COatopcoverage and the stronger interaction with *COatopcompared to commercial Cu, confirming the simulation results. Overall, the work promises an effective approach for boosting CO2R selectivity toward value‐added chemicals.
Enhancing aromatics extraction by double salt ionic liquids: Rational screening‐validation and mechanistic insights
Authors: Xie Kunchi , Chen Jiahui , Cheng Jie , Wang Ruizhuang , Cheng Hongye , Qi Zhiwen , Zhu Kake , Song Zhen 
Published: November 2023

AbstractDespite offering remarkable advantages as solvents, double salt ionic liquids (DSILs) have been scarcely studied for extractive dearomatization from hydrocarbons as well as many other applications, thus urging a theoretical guidance method. In this work, a systematic framework combining the rational screening validation and mechanistic analysis is proposed for tailoring DSILs for the o‐xylene/n‐octane separation. From an initial pool of commercially available ionic liquids (ILs), key thermodynamic properties of paired DSILs are predicted by COSMO‐RS while their important physical properties are estimated from those of corresponding parent ILs (retrieved from experimental database or predicted by a deep learning model). Promising DSILs are tested by liquid–liquid equilibrium experiments, wherein the effect of ion ratio is also evaluated. The mechanism underlying the tunability of DSIL thermodynamic properties is disclosed by quantum chemistry calculation and molecular dynamics simulation. This work can be a valuable reference for guiding the design of DSILs for diverse applications.
Impact of dupilumab on medical readiness in a military population
Authors: Hill Gregory S. , Noller Michael W. , Olubajo Cristianah O. , Tolisano Anthony M. , Riley Charles A. , Fischer Jakob L. 
Published: November 2023

Key Points
Military servicemembers reported high satisfaction rates of dupilumab treatment for CRSwNP.
Some service members fear that dupilumab treatment may limit their career progression.
Updated guidelines are needed for servicemembers to make decisions regarding dupilumab.
Enzymatic Fluoromethylation as a Tool for ATP‐Independent Ligation
Authors: Peng Jiaming , Hughes Gregory R. , Müller Manuel M. , Seebeck Florian P. 
Published: November 2023

AbstractS‐adenosylmethionine‐dependent methyltransferases are involved in countless biological processes, including signal transduction, epigenetics, natural product biosynthesis, and detoxification. Only a handful of carboxylate methyltransferases have evolved to participate in amide bond formation. In this report we show that enzyme‐catalyzed F‐methylation of carboxylate substrates produces F‐methyl esters that readily react with N‐ or S‐nucleophiles under physiological conditions. We demonstrate the applicability of this approach to the synthesis of small amides, hydroxamates, and thioesters, as well as to site‐specific protein modification and native chemical ligation.
Gram‐level NH3 Electrosynthesis via NOx reduction on a Cu Activated Co Electrode
Authors: Liu Dong‐Xue , Meng Zhe , Zhu Yong‐Fu , Sun Xue‐Feng , Deng Xin , Shi Miao‐Miao , Hao Qi , Kang Xia , Dai Tian‐Yi , Zhong Hai‐Xia , Yan Jun‐Min , Jiang Qing 
Published: November 2023

AbstractAmbient electrochemical ammonia (NH3) synthesis is one promising alternative to the energy‐intensive Haber–Bosch route. However, the industrial requirement for the electrochemical NH3 production with amperes current densities or gram‐level NH3 yield remains a grand challenge. Herein, we report the high‐rate NH3 production via NO2− reduction using the Cu activated Co electrode in a bipolar membrane (BPM) assemble electrolyser, wherein BPM maintains the ion balance and the liquid level of electrolyte. Benefited from the abundant Co sites and optimal structure, the target modified Co foam electrode delivers a current density of 2.64 A cm−2 with the Faradaic efficiency of 96.45 % and the high NH3 yield rate of 279.44 mg h−1 cm−2 in H‐type cell using alkaline electrolyte. Combined with in situ experiments and theoretical calculations, we found that Cu optimizes the adsorption behavior of NO2− and facilitates the hydrogenation steps on Co sites toward a rapid NO2− reduction process. Importantly, this activated Co electrode affords a large NH3 production up to 4.11 g h−1 in a homemade reactor, highlighting its large‐scale practical feasibility.
Copper(I)‐Catalyzed Asymmetric Allylation of Ketones with 2‐Aza‐1,4‐Dienes
Authors: Pan Zhi‐Zhou , Li Jia‐Heng , Tian Hu , Yin Liang 
Published: November 2023

AbstractCatalytic asymmetric allylation of ketones under proton‐transfer conditions is a challenging issue due to the limited pronucleophiles and the electrophilic inertness of ketones. Herein, a copper(I)‐catalyzed asymmetric allylation of ketones with 2‐aza‐1,4‐dienes (N‐allyl‐1,1‐diphenylmethanimines) is disclosed, which affords a series of functionalized homoallyl tertiary alcohols in high to excellent enantioselectivity. Interestingly, N‐allyl‐1,1‐diphenylmethanimines work as synthetic equivalents of propanals. Upon the acidic workup, a formal asymmetric β‐addition of propanals to ketones is achieved. An investigation on KIE effect indicates that the deprotonation of N‐allyl‐1,1‐diphenylmethanimines is the rate‐determining step, which generates nucleophilic allyl copper(I) species. Finally, the synthetic utility of the present method is demonstrated by the asymmetric synthesis of (R)‐boivinianin A and (R)‐gossonorol.
Molecular Sieving of Propyne/Propylene by a Scalable Nanoporous Crystal with Confined Rotational Shutters
Authors: Wan Jingmeng , Zhou Hao‐Long , Hyeon‐Deuk Kim , Chang I‐Ya , Huang Yuhang , Krishna Rajamani , Duan Jingui 
Published: November 2023

AbstractSoft porous coordination polymers (PCPs) have the remarkable ability to recognize similar molecules as a result of their structural dynamics. However, their guest‐induced gate‐opening behaviors often lead to issues with selectivity and separation efficiency, as co‐adsorption is nearly unavoidable. Herein, we report a strategy of a confined‐rotational shutter, in which the rotation of pyridyl rings within the confined nanospace of a halogen‐bonded coordination framework (NTU‐88) creates a maximum aperture of 4.4 Å, which is very close to the molecular size of propyne (C3H4: 4.4 Å), but smaller than that of propylene (C3H6: 5.4 Å). This has been evidenced by crystallographic analyses and modelling calculations. The NTU‐88o (open phase of activated NTU‐88) demonstrates dedicated C3H4 adsorption, and thereby leads to a sieving separation of C3H4/C3H6 under ambient conditions. The integrated nature of high uptake ratio, considerable capacity, scalable synthesis, and good stability make NTU‐88 a promising candidate for the feasible removal of C3H4 from C3H4/C3H6 mixtures. In principle, this strategy holds high potential for extension to soft families, making it a powerful tool for optimizing materials that can tackle challenging separations with no co‐adsorption, while retaining the crucial aspect of high capacity.
Über die Passivierung der Metalle und ihre Abhängigkeit vom Lösungsmittel
Authors: Isgasischew N. 
Published: November 2023

Abstract1. Es wurden die Fälle der Passivität von Ni, Co, Fe, Cd, Cu in Alkoholen und teilweise in Wasser untersucht.2. Es wurde die Geschwindigkeit der Passivierung in ihrer Abhängigkeit von verschiedenen Versuchsbedingungen untersucht.3. Es wurde das Auftreten löslicher Peroxyde als Zwischenprodukte des Passivierungsvorganges von Ni, Co, Fe und Cd bewiesen.4. Die Hauptursache der Passivierung von Ni, Co, Fe und Cd in alkoholischer Lösung ihrer Salze ist in der Bildung von deckenden Oxyden zu suchen.5. Die Passivität des Kupfers in Kupferchloridlösung wird durch das Auftreten komplexer Verbindungen von Kupferchlorid und Alkohol und ihrem Einfluß auf die Geschwindigkeit des Elektrodenvorganges bedingt.Die Versuche über die Passivität in verschiedenen Lösungsmitteln sowie auch in deren Mischungen werden fortgesetzt.Die vorliegende Arbeit ist im physikalisch‐chemischen Laboratorium des Moskauer Kommerz‐Instituts ausgeführt worden. Es ist mir eine angenehme Pflicht, Herrn Prof. Dr. N. Schilow für seine wertvollen Ratschläge sowie für sein freundliches Interesse meinen innigsten Dank auszusprechen.
Über periodische chemische Reaktionen I
Authors: Bonhoeffer K. F. 
Published: November 2023

AbstractWährend in einfachen homogenen chemischen Reaktionen bei Kenntnis des Ausgangsgemisches die Angabe der Konzentration eines Reaktionsteilnehmers genügt, um den Fortschritt der Reaktion zu bestimmen, ist bei periodischen Reaktionen mindestens die Angabe zweier unabhängiger Konzentrationen x und y nötig. Damit Perioden auftreten, müssen die Funktionen dx/dt = f (x, y) und dy/dt = g (x, y) bestimmten Bedingungen genügen, die erläutert werden. Die Verhältnisse liegen formal analog wie bei der Selbsterregung elektrischer Schwingungen, wobei die reaktionskinetischen Differentialgleichungen den Differentialgleichungen für die Induktionsspannung und dem Kondensatorstrom entsprechen. Der “fallenden Charakteristik” entspricht eine Art “Autokatalyse”. Es wird weiterhin gezeigt, wieso in heterogenen Systemen die Vorbedingungen für das Auftreten von periodischen Reaktionen besonders günstig liegen und wieweit auf Grund der allgemeinen Reaktionskinetik das Auftreten von “Kippschwingungen” zu erwarten ist.
Über die synthetische Gewinnung von Chrysoberyll. 84. Mitteilung über aktive feste Stoffe von R. Fricke und Mitarbeitern
Authors: Schröuder Wilhelm 
Published: November 2023

AbstractChrysoberyll bildet sich aus einer einfachen Mischung der Oxydkomponenten auch bei 1400° C nur sehr unvollkommen, und zwar auch bei Verwendung aktiver Oxyde. Dagegen bildet es sich aus einer richtig hergestellten stöchiometrischen Mischfällung von α‐Be(OH)2 und γ‐Al OOH schon bei 1200° C vollkommen glatt. Eine Reihe von Nebenerscheinungen der Reaktion werden mit der Emaniermethode verfolgt.
Zur Methodik der Messung von Flammengeschwindigkeiten
Authors: Bartholomé E. , Bartholomé E. 
Published: November 2023

AbstractDie Methode zur Messung von Flammengeschwindigkeiten durch Ausmessen des Innenkegels eines Bunsenbrenners wird in der Weise abgewandelt, daß man das brennbare Gasgemisch nicht aus einem glatten Rohr, sondern aus einer Düse abbrennen läßt. Man erhält so über einen größeren Teil des Düsenquerschnittes eine konstante Ausströmungsgeschwindigkeit. In diesem Teil ist die Flammenfläche wirklich ein Kegelmantel, aus dessen Neigungswinkel man die Flammengeschwindigkeiten berechnen kann. Die Ausströmung aus einem Düse hat gegen‐über der Ausströmung aus einem langen glatten Rohr außerdem den Vorzug, daß man diese Strömung leicht bis zu Reynoldsschen Zahlen von >4000 laminar halten kann, so daß es mit dieser Anordnung möglich ist, sehr schnell brennende Flammen zu messen, was offensichtlich bisher nicht einwandfrei gelungen war.Nach dieser Methode wurden die Gemische von H2, C2H2, C2H4 und C3H8 mit O2, von H2 mit Cl2 und von H2, C2H2, C2H4 und C3H8 mit Luft gemessen. Soweit Messungen nach der alten Methode zum Vergleich herangezogen werden konnten, sieht man, daß die alten Werte alle niedriger liegen als die mit der neuen Methode bestimmten. Es zeigt sich aber, daß die Abweichungen der beiden Methoden voneinander unabhängig von der Flammengeschwindigkeit und relativ konstant sind, so daß die zahlreichen, nach der alten Methode gewonnenen Ergebnisse von Flammengeschwindigkeiten sich mit ziemlicher Genauigkeit in die richtigen Werte umrechnen lassen.
Über den Einfluß des in der Palladium‐Elektrode gelösten Wasserstoffs auf die Wasserstoffüberspannung
Authors: Hitzler† M. , Knorr C. A. , Mertens F. R. 
Published: November 2023

AbstractEine mit höherer Stromdichte kathodisch vorpolarisierte und dadurch übersättigte Palladiumelektrode zeigt nach Stromöffnung, wie bekannt, eine lebhafte Gasentwicklung, die mit abnehmender Intensität längere Zeit andauert. Wir haben diese für die Theorie der Wasserstoffüberspannung aufschlußreiche Erscheinung näher untersucht. Bestimmt wurde zunächst unter Stromfluß im stationären Zustand die Überspannung in Abhängigkeit von der Stromdichte und dann nach Stromöffnung der zeitliche Abfall des negativen Potentials sowie die sich dabei nachentwickelnde Gasmenge.Die Versuche wurden von M. Hitzler1) und F. R. Mertens2) durchgeführt.
Kinetik unvollständiger Verbrennungsvorgänge von Systemen mit NO2, insbesondere Tetranitromethangemischen
Authors: Behrens Hans 
Published: November 2023

AbstractDie bei der Verbrennung von flüssigen Gemischen aus organischen Substanzen und Tetranitromethan gewonnenen Ergebnisse über Stickoxydgehalt der Flammengase, Rußbildung und Abbrandgeschwindigkeiten werden mitgeteilt. Unter Normaldruck findet nur eine unvollständige Verbrennung statt, so daß kein chemisches Gleichgewicht zwischen den Reaktionsprodukten vorliegt.Im theoretischen Teil werden insbesondere die Kinetik der Stickoxyd‐, Kohlendioxyd‐ und Wasserbildung untersucht, wobei es gelingt, auf Grund der kinetischen Daten einiger Elementarreaktionen die experimentellen Befunde, die sich einer Erfassung mit Hilfe der Thermodynamik verschließen, verständlich zu machen.
Thermodynamik des Pyritzerfalls
Authors: Wunderlich Günter 
Published: November 2023

AbstractDurch Vergleich thermodynamischer Gleichgewichtsberechnungen mit experimentellen Daten wird die Molekülgroöße des beim Pyritzerfall entstehenden Schwefels erhalten. Damit ist die genaue Berechnung des Dissoziationsdruckes im Temperaturgebiet 300–950° K möglich.